Solutions:, The Exponential
Solutions:, The Exponential
Solutions:, The Exponential
Chapter 2
At shorter distances, the ionic molecule is more stable. For r , the exponential
term for the repulsion in the two given potential functions can be neglected, so that
in the case of the ionic molecule, essentially only the Coulomb interaction remains:
e2
Pi (r) = − + IE . (2)
4π ε0 r
With the simplification C = 0, it follows that Pn (r) = 0, and thus from (1) and
(2) we obtain the determining equation for the distance r0 :
e2
− + IE = 0 , (3)
4π ε0 r
e2
r0 = . (4)
4π ε0 I E
With I E = 1.42 eV, one finds
r0 = 1.01 · 10−9 m .
2.2 In order to obtain the best possible resolution in the transmission electron
microscope, i. e. the smallest possible value of dp , one chooses an electron beam
intensity (dose I) which approaches the threshold for damage of the molecules,
(I = Ncr ). Furthermore, the necessary signal/noise ratio S/N is minimised. If these
two factors have been optimised, the remaining possibility is to increase the contrast
Cn by stacking many monolayers upon each other. Cn is proportional to the square
root of the number n of layers, so that with the contrast C1 = C for a single
monolayer, we find:
√
Cn = n C . (1)
2 Solutions
The theoretical point resolution can be calculated using the formula of Freyer:
S/N
dp = √ √ , (2)
nC f I
where f is the electron yield factor (0.25). At the required resolution of dp = 1 Å,
this yields the number n of monolayers which will generate the necessary contrast:
(S/N)2
n= . (3)
dp2 C 2 f I
With the given data for the microscope, one thus finds
n = 100
If we choose the time of the ionisation as the zero point of the time scale,
then the apparatus registers a maximum at the time T (in the ideal case as a δ-
function), which indicates the arrival of the large molecule. An accelerating voltage
of U d − Us = 2 kV, on the assumption that every molecule is only singly ionised
(n = 1), yields
T = 5.1 · 10−5 s .
The time dependence of the current from the detector in fact exhibits a number
of maxima for t < T , which are caused by solvent molecules as well as by fragments
of the large molecules.
Chapter 2 3
2.4 The number of C60 molecules which form a Langmuir film with a surface
area A can be computed from the volume V of the solution with a molar particle
concentration of c:
n = cV . (1)
If the film consists of a single monomolecular layer, the average area AM per
molecule is found to be
A A
AM = = . (2)
n cV
With the experimental values given, this means that
The area of a C60 molecule defined by the van der Waals interaction is 78.5 Å2 .
Considering that even for spherical closest packing, the space per molecule required
is somewhat more than this area, one arrives at a value which is about four times
greater per molecule than the available area AM . This means that the film consists
of four stacked monolayers of C60 molecules.
2.5 In the experimental method given, the osmotic pressure is compensated by the
hydrostatic pressure p of a solution of density = 0.867 g/cm3 and height h:
p = gh. (1)
g h = c NA k T (1 + α c) . (2)
2.6 The specific heat C V of a material at constant volume is defined as the derivative
of its internal energy U with respect to the temperature:
dU
CV = . (1)
dT dV =0
Using the differential expression for the internal energy,
dU = T dS − p dV + µ dN , (2)
and dN = 0, we obtain from (1) and from the entropy S per degree of freedom,
1
S= k ln T (3)
2
the specific heat per molecule and degree of freedom:
∂S k
CV = T = . (4)
∂T 2
For a molecule with f degrees of freedom, we thus find
k
CV = f · . (5)
2
In analogy to the derivation of C V from the internal energy U, one finds the
specific heat C P at constant pressure from the enthalpy H = U + pV . Per molecule
we obtain
C P = CV + k . (6)
Chapter 2 5
Chapter 3
3.1 a) The electrostatic energy of the system of N independent rigid dipoles due
to their interaction with the externally applied field E is given by
N
H=− p E cos θi . (1)
i=1
The distribution density of the angles θ between the dipoles and the direction of
the field, using the notation β = 1/k T , is assumed to be given by
1 −β H(θ)
f(θ) = e (2)
Z
with the density of states (partition function)
+1
Z= e−β H(θ) d N (cos θ) . (3)
−1
along the direction of the external field E can be found by using the distribution
function f from (2); it is
+1 N
P= f(θ) p cos θi d N (cos θ) . (5)
−1 i=1
With (1), (2) and (3) and employing the substitutions u i = cos θi and x = β p E,
this becomes
+1 +1 −1
P=Np xu
u e du xu
e du . (6)
−1 −1
E → ∞.
In order to orient the dipole precisely along the field direction, one would thus have
to apply an infinitely strong electric field!
c) The function coth can be expanded in a series according to
1 x x3 2 x5
coth(x) = + − + + . . . for 0 < |x| < π . (12)
x 3 45 945
For sufficiently small |x|, the series can be terminated after the first-order term
in x, thereby simplifying the Langevin function L(x) in (9) to
x
L(x) → . (13)
3
If the orientation polarisation reaches 50% of its theoretical maximum value,
then from (8) we find
L(x) = 0.355
3.2 The water molecule represents an electric dipole ( p = 1.85 D = 6.17 · 10−30
Cm) with a negative partial charge on the O atom and a positive charge between the
H atoms. In the presence of a (negative) anion, the molecule will therefore orient
itself with its H atoms pointing towards the ion.
The molecule is considered in the following as a dipole of length d, consisting
of a positive and a negative elementary charge. The electrostatic potential of a point
charge q at a distance r is
q
φ= (1)
4π ε0r
and produces a field
dφ q
E=− = . (2)
dr 4π ε0 r 2
The distance from the two point-like elementary charges q = ±e to the (also
point-like) anion is r ∓ d/2. At the position of the anion, the fields produced by the
two point charges then superpose to give
e e
E(r) = − (3)
4π ε0 (r − d/2) 2
4π ε0 (r + d/2)2
pr
E(r) = 2 (4)
2π ε0 r 2 − d 2 /4
with p = d r. From the given dipole moment, one finds a dipole length of d =
3.85 · 10−11 m, so that d 2 /4 can be neglected in comparison to r 2 :
p
E(r) = . (5)
2π ε0 r 3
For the distances given, one finds the following field strengths at the position of
the anion:
a) at r = 10−9 m : E = 1.11 · 108 V/m
b) at r = 3 · 10−10 m : E = 4.11 · 109 V/m
c) at r = 3 · 10−8 m : E = 4.11 · 103 V/m
3.6 At optical frequencies, the reorientation of the molecules can no longer follow
the rapid changes in the applied field, so that the orientation polarisation becomes
negligibly small. The Debye equation (cf. Problem 3.4) can then be simplified to the
Clausius-Mosotti equation with ε = n 2 :
n2 − 1 M NA α
Pm = = . (1)
n +2
2 3ε0
Solving for α and using α = α/4π ε0 , one obtains from the given index of
refraction n = 1.333 with the molecular mass M = 18.015 g/mole and the density
= 0.9982 g/cm3 the polarisability volume
α = 1.47 · 10−30 m3 .
3.7 The dipole moment pH2 O of the water molecule can be treated as the vector sum
of the dipole moments pOH of two OH bonds. The dipole moments perpendicular
to the plane of symmetry compensate each other, while the parallel components
superpose constructively:
φ
pH2 O = 2 pOH cos , (1)
2
so that with pH2 O = 1.85 D and φ = 104.25◦ , it follows that:
φ
pH2 O2 = 2 pOH cos , (3)
2
Chapter 3 11
where φ is the angle between the two OH groups in the two-dimensional projection.
With pH2 O2 = 2.13 D, we obtain
φ = 90.3◦ .
From εfl = 1 + χfl = 78.5 for liquid water of density 1 g/cm3 , one thus finds for
water vapour at 1 bar
and thus
19% relative humidity at 40 ◦ C already exhibits the same effect on the value of ε as
does dry air alone.
3.9 The Debye equation, (3.19), for the molar polarisability Pm makes the connex-
ion between a macroscopically measurable quantity, the dielectric constant ε, and the
microscopic quantities dipole moment p0 and polarisability volume α = α/4π ε0
of chloroform.
Fig. S.1. A graph of the molar polarisability Pm of CHCl3 vs. the inverse temperature, 1/T :
data points and fitted line
12 Solutions
If one plots Pm against 1/T , then for temperatures above the melting point TS =
−64 ◦ C of chloroform, one obtains approximately a straight line with a y-intercept
a and a slope b. Below TS , the orientation polarisation is frozen in, so that its
contribution to Pm (i. e. the term containing the permanent dipole moment p0 )
vanishes. For 1/T > 1/TS , Pm is therefore practically independent of temperature and
lies on a straight line parallel to the x-axis in the plot. For T → ∞ the contribution
from the orientation polarisation likewise vanishes, so that the y-intercept a in the
plot should have the value of the constant ε for 1/T > 1/TS . For fitting the line to
the data points in the plot, we thus use only the first three points and the required
intercept on the y-axis.
From the slope b = 4508.5 cm3 K/mole, we can compute the dipole moment of
chloroform
p0 = 2.87 · 10−30 Cm = 0.86 D
and from the intercept a = 30.0 cm3 /mole its polarisability volume
α = 11.89 · 10−30 m3 .
3.12 The dielectric function of the NaCl crystal (Fig. S.2) is based on the model
of a coupled photon-phonon field (polaritons). From the given values, one finds
and then obtains the following frequency dependence for the dielectric constant ε:
An effect of the photon-phonon coupling is the formation of a frequency√ gap:
for ΩTO < ω < ΩLO , ε is negative and thus the wave vector k = ω ε(ω)/c is a
purely imaginary quantity, so that in this frequency range, the wave is damped in a
NaCl crystal as e−|k|x . In the neighbourhood of ΩTO , |k| is large, the wave penetrates
only a very short distance into the crystal, and it is completely reflected. For ω near
ΩLO , it is less strongly damped and can pass through a thin NaCl sheet (although
attenuated). The transmitted rays are the so called residual radiation. More about
this subject can be found in textbooks on solid-state physics.
Chapter 4
4.1 a) The time-independent Schrödinger equation in regions I, II, and III can be
written in the following ways:
2m
I) ∂ 2 ψ (1) /∂x 2 − κ 2 ψ (1) = 0, κ2 = (V0 − E) , (1)
2
2m
II) ∂ 2 ψ (2) /∂x 2 − k2 ψ (2) = 0, k2 = 2 E , (2)
2m
III) ∂ 2 ψ (3) /∂x 2 − κ 2 ψ (3) = 0, κ = 2 (V0 − E) .
2
(3)
It follows from (1) and (3) that
2m
k2 + κ 2 = V0 = C . (4)
2
Chapter 4 15
V(x)
Ι ΙΙ ΙΙΙ
x
–a a
b) Boundary conditions:
lim ψ (1) (x) = 0 , therefore B (1) = 0 , (5)
x→−∞
These are two homogeneous linear equations for A(2) , B (2) . The condition that
they have a non-trivial solution is that the determinant of the coefficients vanishes,
i. e.
N
A(2) = B (2) = ; A(1) = B (3) = Neκa cos(ka) , (14)
2
and thus
κ(x+a)
e cos ka (I)
ψs (x) = N cos kx (II) . (15)
κ(−x+a)
e cos ka (III)
N
A(2) = −B (2) = , A(1) = −B (3) = −Neκa sin(ka) (17)
2
and thus
κ(x+a)
−e sin ka (I)
ψa (x) = N sin kx (II) . (18)
κ(−x+a)
e sin ka (III)
3) Normalisation:
+∞ −a
!
1 = |(x)| dx = ψ (1) (x) 2 dx
2
−∞ −∞
+a ∞
(2) 2
+ ψ dx + ψ (3) (x) 2 dx . (19)
−a a
0
0 5 10
k
15
10
In the symmetric case, α), there is at least one intercept, independently of a; the
ground state is symmetric.
d) The limiting case V0 → ∞:
For V0 → ∞, C → ∞ also holds, and due to (1) and (3), we have also
κ → ∞. (24)
β) cot(ka) = ∞, i. e.
π
kn = n , n ∈ N or (28)
a
πn
kn = , n even , (29)
2a
1 sin kn x (II)
ψa = √ (30)
a 0 (I, III) .
2 kn2 2 π 2 2
En = = n , n ∈ N. (31)
2m 8ma2
Matrix elements: the integrals are elementary.
a
xnm = xψn ψm dx = 0 (32)
−a
for n and m even or n and m odd. This result also follows from symmetry consider-
ations.
n odd, m even:
n+m−1 16anm
xnm = (−1) 2 , (33)
π 2 (n 2 − m 2 )2
(x 2 )nm = 0 (34)
n, m odd, n = m:
n−m 32a2 nm
(x 2 )nm = (−1) 2 , (35)
(n 2 − m 2 )2
n, m even, n = m:
n−m 32a2 nm
(x 2 )nm = (−1) 2 , (36)
π 2 (n 2 − m 2 )2
n = m:
a2 2a2
(x 2 )nn = − 2 2. (37)
3 n π
Momentum matrix elements:
a
d
pnm = ψn ψm dx = 0 (38)
i dx
−a
where
E 3 − E 1 = 8ω0 , (46)
x = p = 0 , (47)
2 2 1 8 3
x =a + − cos(8ω0 t) . (48)
3 9π 2 2π 2
Correspondingly,
2
y = a2 (11)
and
2
z = a2 . (12)
Chapter 4 21
(11) and (12) also follow directly from (10) due to the spherical symmetry of (1).
Momentum expectation values:
p x = p y = pz = 0 (13)
∂ 1x
ψ100 = − ψ100 , (14)
∂x ar
∂2 1 1 x2 x2
ψ100 = − − − ψ100 , (15)
∂x 2 a r r3 ar 2
p2x = ψ100 | p2x |ψ100
∞ π 2π
2
= dr dθ dφe−2r/a r 2 sin θ
πa4
0 0 0
1 cos2 φ sin2 θ cos2 φ sin2 θ
×
r − −
(16)
! r ! a !
(1) (2) (3)
(1) yields
∞
42 2
e−2r/a rdr = ; (17)
a4 a2
0
(2) yields
∞ π
2 −2r/a
− 4 dre r sin3 θdθ , (18)
a
0 0
∞
42 1 2
=− 4 dre−2r/a r = − ; (19)
3a 3 a2
0
and
1/2
∆x = x 2 − x 2 , (24)
2
E kin = ψ100 | − ∆ |ψ100 . (27)
2m
The Laplace operator in spherical polar coordinates is given by
d2 2 d l(l + 1)
∆= + − , (28)
dr 2 r dr r2
2
E kin = . (29)
2ma2
e2 1 e2
E pot = ψ100 | − |ψ100 = − . (30)
4πε0r 4πε0 a
Expectation values for the angular momentum:
a) Normalisation:
∗
|ψ± | dV = c 2 ± 2 dVφa φb
2 2
!
= c2 (2 ± 2S) = 1, and thus
−1/2
c = [2(1 ± S)] . (2)
The factors of 2 in (4) and (5) result from the fact that in E (3), there were originally
two further integrals in which the indices a and b were exchanged relative to (4) and
(5), but which otherwise were identical to (4) and (5) from symmetry considerations.
Using the abbreviations E 0 , C, D, S as in the text, we find
1 0
E= E + C ± S · E0 + D . (6)
1±S
This can be brought into the form
C±D
E = E0 + . (7)
1±S
c) with the trial solution
ψ = c1 φa + c2 φb (8)
and thus
Chapter 4 25
1
ψ=& (c1 φa + c2 φb ) . (10)
c21 + c22 + 2c1 c2 S
!
:=N
∂ Ẽ
(i) = 2N 2 (c1 C + c2 D)
∂c1
!
− 2N 4 (c1 + c2 S)[(c21 + c22 )C + 2c1 c2 D] = 0 , (13)
∂ Ẽ
(ii) = 2N 2 (c2 C + c1 D)
∂c2
!
− 2N 4 (c2 + c1 S) [ c21 + c22 C + 2c1 c2 D] = 0 . (14)
We take
(i)c2 − (ii)c1
4
= 0 = c21 − c22 S[ c21 + c22 C + 2c1 c2 D] (15)
2N
and thereby obtain
A
ra
R/2
ϑ
(ξ,η,ϕ)
R γ
R/2
rb
so that
Calculation of D yields
2 r 2 sin θ
D= (23)
R ra rb
or, due to (18),
r 2 sin θ
D= . (24)
(R/2)3 (ξ + η)(ξ − η)
The volume element dV (19), applying (21, 24), is given by
3
R 2
dV = ξ − η2 dξdηdφ , (25)
2
Chapter 4 27
where
0 ≤ φ < 2π ,
−1 ≤ η < 1 ,
1 ≤ ξ < ∞. (26)
As trial wavefunctions, it is advisable to choose
3/2
1 α αr
φ(r; α) = √ exp − . (27)
π a0 a0
We first set β = α/a0 .
Computation of the overlap integral S:
β3
S = φa φb dV = dV exp [−β (ra + rb )] (28)
π
or, in prolate elliptical coordinates,
3 2π 1 ∞
β3 R
S= dφ dη dξ ξ 2 − η2 exp (−βRξ) . (29)
π 2
0 −1 1
Making use of the ancillary formulas from Problem 4.2, we can carry out the
integration over ξ after combining terms,
) *
1 αR 2 αR αR
S= + + 1 exp − . (31)
3 a0 a0 a0
Evaluation of the integrals using the ancillary formulas of Problem 4.2 and
combining terms, with β = α/a0 , gives:
e2 1 α 1 αR
C= − + + exp −2 . (37)
4πε0 R a0 R a0
The exchange integral D is:
e2 1
D=− φa φb dV
4πε0 ra
e2 β 3 1
=− dV exp [−β(ra + rb )] . (38)
4πε0 π ra
Or, in prolate elliptical coordinates:
3 2π +1 ∞
e2 βR
D=− 2 dφ dη dξ
4π ε0 2
0 −1 1
2 2
× ξ − η2 exp (−βRξ) . (39)
R(ξ + η)
Integration over φ and cancellation of (ξ + η) yields:
1 ∞
e2 β 3 R2
D=− dη dξ(ξ − η) exp (−βRξ) . (40)
8πε0
−1 1
Integration over η:
∞
e2 β 3 R2
D=− dξ ξ exp (−βRξ) . (41)
4πε0
1
Chapter 4 29
Evaluation in spherical polar coordinates: since the wavefunction does not de-
pend on θ and φ, we use
1 ∂ 2∂
∆ = ∆r = r (44)
r 2 ∂r ∂r
and dV = 4πr 2 dr on integrating only over r. Then
r 2 ∆r φa ∝ −2rβ + (βr)2 exp(−βr) . (45)
e2 α ' α (
E0 = −1 . (48)
4πε0 a0 2
e) The total energy is given by:
' (
e2 α α
E mol = −1
4πε0 a0 2
−R−1+(α/a0 + R−1 )e−2αR/a0 ∓(α/a0 )(1 + αR/a0 )e−αR/a0
+
[(1/3)(αR/a0 )2 + αR/a0 + 1]e−αR/a0
2
e 1
+ . (49)
4πε0 R
30 Solutions
E mol
2
1
0
–1
0,8
1
1,2
1,4
R 1,6 0,8
0,9
1,8 1
1,1
2 1,2 α
1,3
Fig. S.7. E mol (49) as a function of α and R (in units of a0 ) for the symmetric state
E mol
10
9
8 antisymmetric
7
6
5
4
3
2
1
0 R
0,5 1 1,5 2 2,5 3 3,5 4 4,5 5
–1
–2 symmetric
Fig. S.8. E mol (49) for fixed α = 1 as a function of R in units of a0 for the symmetric and
the antisymmetric states, resp.
The evaluation must now be carried out numerically, which can be easily done
using a PC (cf. Figs. S.7–9).
f) Computation of the expectation values x, p, x 2 .
In order to express x, y, z in prolate elliptical coordinate, we proceed as follows:
It follows from (18) that
R R
(ξ + η) = ra , (ξ − η) = rb (50)
2 2
Chapter 4 31
E mol
10
9
8 antisymmetric
7
6
5
4
3
2 symmetric
1
0 α
0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2
–1
–2
Fig. S.9. E mol (49) for fixed R = 1.36 a0 as a function of α for the symmetric and the
antisymmetric states
R2 1
(ξ ± η)2 = r 2 + R2 ∓ rR cos θ . (51)
4 4
From this, we find
R2 1
(ξ + η)2 + (ξ − η)2 = 2r 2 + R2 (52)
4 2
and
R2
(ξ + η)2 − (ξ − η2 ) = −2rR cos θ . (53)
4 !
=4ξη
We write
x = dV xψ 2 . (59)
Now, the wavefunction ψ = N(φa + φb ) as well as the expressions (54, 57, 58)
for (x, y, z) and relation (25) for the volume element dV can be inserted into (59). Its
evaluation is, as above, elementary and yields zero for all components. 1 This can also
be concluded directly from symmetry considerations, e. g. for x = dVxψ 2 . Since
ψ(−x, y, z) = ψ(x, y, z), ψ 2 is also invariant with respect to (x, y, z) → (−x, y, z).
On the other hand, the value of the integral must remain unchanged, from which
it follows that x = −x and thus x = 0. The same reasoning also holds for
∂/∂x, ∂/∂y, and ∂/∂z, since e. g. in the transformation (x, y, z) → (−x, y, z),
∂/∂x → −∂/∂x also holds.
In order to obtain a measure of the spatial extension of the wavefunction ψ, one
must compute x 2 , y2 , and z 2 . We illustrate this using as an example z 2 , going
immediately to prolate elliptical coordinates. With
1 X
cosh X ≡ e + e−X , (60)
2
and inserting the expressions for z 2 , ψ, and dV , we obtain
5 2π 1 ∞
2 β3 R
z =2 dφ dη dξ ξ 2 − η2 ξ 2 η2
π 2
0 −1 1
× [cosh(βRη) ± 1] exp (−βRξ) . (61)
Due to (60), all the integrations can be carried out explicitly (first over φ, then
over η, finally over ξ). With β = α/a0 , the result is
' a (2
0
z 2 =
α
1 αR 4 7 αR 3 9 αR 2 αR
+ + +2
30 a0 30 a0 10 a0 a0
1 αR
× e−αR/a0 + +2 . (62)
2 a0
Chapter 4 33
4.4 Conjecture:
1 ∗
Ψ HΨdV1 ...dVn
1 ≥ E0 . (1)
Ψ ∗ ΨdV1 ...dVn
HΦ0 = E 0 Φ0 (2)
Every vector of the space of states can thus be expressed as a linear combination
of the Φ j :
∞
Ψ = ajΦj . (4)
j=0
Inserting (4) into the left side of (1), we obtain using (3)
∞
∞
a2j E j / a2j (5)
j=0 j=0
and due to E j ≥ E 0
∞
∞
∞
∞
a2j E j / a2j ≥ E 0 a2j / a2j = E 0 , (6)
j=0 j=0 j=0 j=0
HΨ = EΨ (1)
be given by
N
H= Hi (2)
i=1
with
and let
2 3
( j)
Hi , φk = 0 , i = j . (4)
We insert
4
N
( j)
Ψk1 ,k2 ...k N = φk j , (5)
j=1
where k1 , . . . k N are a selection from the quantum numbers of (3), into (1) and obtain
with (4)
N 4
N
N 4
i−1 ' ( 4
N
( j) ( j) ( j)
Hi φk j = φk j · Hi φk(i)i φk j , (6)
i=1 j=1 i=1 j=1 j=i+1
N 4
N
( j)
E k(i)i φk j = EΨ (7)
i=1 j=1
with
N
E= E k(i)i . (8)
i=1
and correspondingly for S2± . Then (6) can be cast in the form
From (11) and (12), α(1)α(2) and β(1)β(2) are already eigenfunctions belonging
to S2 with the eigenvalue 22 . To determine the remaining eigenfunction, we add or
subtract equations (12, 13) to or from one another, and obtain
i. e. the spin part of (1) is an eigenfunction of S2 with the eigenvalue 22 . Corre-
spondingly, we find
where x1 = x, x2 = y, x3 = z.
To find the maximum of | ψ |2 , we take:
) *5
∂ψi xj xj 3
= −γ +γb j − γ α(1 − γr)+γ bi xi e−γr . (10)
∂x j r r i=1
From the requirement that ∂|ψi |2/∂x j = 2ψi (∂ψi /∂x j ) = 0, it follows that
3
a(1 − γr) + γ bi xi = 0 (11)
i=1
Chapter 4 37
or
xj = 0 (12)
or
3
x j 1 + a(1 − γr) + γ bi xi = b j r . (13)
i=1
ψ± = ψ2s ± ψ2 px (14)
a = 1, b1 = ±1, b2 = b3 = 0, xi = x, y, z . (15)
We then find
From this, it follows for the maxima of the charge density that
3
y = z = 0, x = ∓ . (19)
2γ
b) Centre of gravity of the charge distribution
Since in (9) ψ2s and
√ψ2 px are normalised and orthogonal to one another, (9) is
to be normalised by 1/ 2:
1
x± = ψ± xψ± , (20)
2
where . . . denotes the integration in spherical polar coordinates r, θ, φ, i. e.
∞ π 2π
2
r dr sin θdθ dφψ± xψ± . (21)
0 0 0
x0 (−1, −1, −1); x0 (−1, 1, 1); x0 (1, −1, 1); x0 (1, 1, −1), (30)
√
which corresponds to the vertices of a tetrahedron with the edge length x0 2 2.
d) With the wavefunctions (1–8), the superpositions corresponding to the hy-
bridisation can be written immediately. In spherical polar coordinates, the integrals
can be evaluated in elementary fashion, and they demonstrate the orthogonality of
the wavefunctions.
Chapter 5 39
Chapter 5
b a
~
b e e
Fig. S.11.
b) Boundary condition at the end of the molecule (Fig. S.11, lower part): a π-
electron can also be located with a certain probability outside the last atom e. (ẽ is
a fictitious atom or “empty cell” at which φ can decay to zero).
φbe (e) = φeẽ (e) , (4)
φeẽ (ẽ ) = 0 , (5)
φbe (e) = φe ẽ (e) . (6)
c) The butadiene molecule:
2 d 2
Heff = − + V(x)
2m dx 2
0 for 0 ≤ x ≤ 5d
with V(x) = . (7)
∞ otherwise
40 Solutions
Chapter 6
4 3 4 3
1 a 2 1 2
Fig. S.14. Triangle in a square. Case 3
6 6
b Fig. S.15. Triangle in a square. Case 4
7
5 7 5
4 3 4 3
Chapter 6 41
b) When two symmetry operations are carried out in succession, the result again
corresponds to a symmetry operation, as one can show by examining all the possible
combinations. The inverse of a symmetry operation is clearly itself a symmetry
operation. One can directly demonstrate the validity of the associative law by first
taking A · B and then (A · B) · C, or first B · C and then A · (B · C), noting that
(A · B) · C = A(B · C), where A, B, C are symmetry operations. It is sufficient to
examine a few examples.
The identification as a group can be carried out systematically, simply and in an
elegant manner by considering that each symmetry operation can be represented by
a permutation of the vertices and that the permutations form a group.
c) Interaction potentials
In Fig. S.12: the spacings are:
√
d1(1) ≡ r12 = a, d2(1) ≡ r24 = 2a, d3(1) ≡ r56 = b ,
a
d4(1) ≡ r57 = 2b, d5(1) ≡ r16 = √ ,
2
%
(1)
d6 ≡ r45 = a − 2ab + 2b ,
2 2
%
d7(1) ≡ r15 = a2 + 2ab + 2b2 .
V (1) = 14(a2 + b2 ) .
In Fig. S.13:
√
d1(2) ≡ r12 = a, d2(2) ≡ r24 = 2a, d3(2) ≡ r56 = b ,
a a
d4(2) ≡ r57 (2) (2)
= 2b, d5 ≡ r16 = √ , d6 ≡ r45 = b − √ ,
2 2
a a + 2b
2 2
d7(2) ≡ r25 = b + √ , d8(2) ≡ r17 = .
2 2
V (2) = 14(a2 + b2 ) .
In Fig. S.14:
√
d1(3) ≡ r12 = a, d2(3) ≡ r24 = 2a, d3(3) ≡ r56 = b ,
& √
1
d4(3) ≡ r45 = √ 3a2 − (3 + 3)ab + 2b2 ,
6
&
1 √
d5(3) ≡ r46 = √ 3a2 + 2 3ab + 2b2 ,
6
& √
1
d6(3) ≡ r47 = √ 3a2 + (3 − 3)ab + 2b2 ,
6
&
1 √
d7(3) ≡ r16 = √ 3a2 − 2 3ab + 2b2 ,
6
& √
1
d8(3) ≡ r15 = √ 3a2 − (3 − 3)ab + 2b2 ,
6
& √
1
d9(3) ≡ r17 = √ 3a2 + (3 + 3)ab + 2b2 .
6
(3)
V = 4V(1) + 2V(2) + 3V(3) + 2V(4) + 2V(5)
+ 2V(6) + 2V(7) + 2V(8) + 2V(9) .
In fig. S.15:
√
d1(4) ≡ r12 = a, d2(4) ≡ r24 = 2a, d3(4) ≡ r56 = b, d4(4)
b a
≡ r45 = √ − √ ,
3 2
& &
a2 ab √ √ b2
d5(4) ≡ r46 = +√ 2+ 3− 2− 3 − ,
2 12 3
b a
d6(4) ≡ r25 = √ + √ ,
3 2
& &
(4) a 2 ab √ √ b2
d7 ≡ r26 = +√ 2− 3− 2+ 3 − ,
2 12 3
(4) a2 b2
d8 ≡ r15 = − ,
2 3
Chapter 6 43
& &
a2 ab √ √ b2
d9(4) ≡ r16 = −√ 2− 3+ 2+ 3 − ,
2 12 3
& &
(4) a2 ab √ √ b2
d10 ≡ r17 = +√ 2− 3+ 2+ 3 − .
2 12 3
1,6
1,2
V1 – V2
0,8
0,4
0
0 0
1 1
2 2
~ 3 3 ~
b 4 4 a
5 5
Fig. S.16. The potential difference V 1 − V 2, where V 1 = V (1) with V(r) = 1 − e(−r)
0,2
0
–0,2
–0,4
V2 – V4
–0,6
–0,8
–1
–1,2
–1,4
0
0 1
0,5 1 2
1,5 3
2 2,5 4 ~
~ 3 3,5 5 a
b
2
V4 – V2
–1
0 1 2 1 0
3 4 3 2
~ 5 5 4 ~
b a
The same method of summation over the elements of the group is the basis of
the orthogonality relations which we now discuss.
Let
0,3
V3 – V4
0,2
0,1
0
0 0
1 1
2 2
~ 3 3 ~
b 4 4 a
5 5
and write
where the sum runs over all the elements R of the group. Then B remains unchanged
under the following transformation:
Proof :
due to the properties of the representations. If the sum in (6) runs over all the elements
R, so then so does R = RR0 , with R0 fixed. From I of the general theorem, it follows
that the matrix B = 0, i. e.
46 Solutions
u ik (R)akl v̂ lm (R) = 0 . (11)
R kl
Since the akl are arbitrary, the following g2 · g 2 equations result:
u ik (R)v̂ lm (R) = 0 (12)
R
i. e.
where the constant α still depends on the matrix A. We set all the elements in the
matrix A equal to zero except for one, akl = 1 for a particular pair of values k, l. It
then follows that
u ik (R)û lm (R) = αkl δim . (17)
R
In (17), we set m = i and sum over m = 1, 2, ..., g, obtaining then for the left
side of (17)
u mk (R)û lm (R) (19)
R m
hδlk . (21)
gαkl . (22)
where then αkl is determined by the order h of the group and the dimension g of the
matrix representation. We thus obtain the first main result:
1
1 for i = m, k = l
u ik (R)û lm (R) = g (24)
h 0 otherwise
R
and
û ll (R) = χ̂(R) (27)
l
or
v̂ ll (R) = χ̂ (R) (28)
l
and obtain
1
χ(R)χ̂(R) = 1 . (29)
h R
The expressions χ̂(R) or χ̂ (R) can be cast in a different form. If the represen-
∗
tation matrices are unitary, it holds that û lm = vml and χ̂ = χ ∗ follows, where
the
asterisk denotes complex conjugate quantities. Furthermore, U −1 (R) = U R−1
and therefore
û lm (R) = u lm R−1 . (31)
6 6
6.3 We apply Pk = |kmkm| to |v = cln |ln. Due to the orthogonality
m ln
relation (37) from problem 6.4, we find immediately
Pk |v = ckn |kn .
n
is a projection operator, which projects the space of the basis vectors of the repre-
sentation onto the subspace of the irreducible representation j with the character χ j .
Making use of Dirac’s bra and ket notation, we denote the basis vectors by
|k, m , (36)
where k refers to the subspace of the irreducible representation k, and m to the vector
considered within this space. k thus distinguishes the blocks in Fig. 6.14. We first
treat the case that all the blocks belong to different irreducible representations. We
consider unitary representations and therefore can assume the orthonormalisation
We now insert I (38) into (35) before and after R and obtain
1
χ̂ j (R) |k, m k, m| R |l, n l, n| . (39)
k R k,m l,n
Keeping the bra and ket notation in mind, we obtain in (39) the matrix element
where the Kronecker delta δkl results from the zeroes outside the blocks in Fig. 6.14.
Making use of the definition of the group character, χ̂ j (R), we write
j
χ̂ j (R) = δµν û µν (R) . (41)
µν
Employing (40) and (41), (39) can be brought into the form:
1 j
δµν û µν (R)u km,n |k, m k, n| . (42)
µν k,m,n
h R
Due to (37), P j is clearly a projection operator onto the subspace j. Here, we use
χ̂ j (R), which is the same for equivalent representations.If several such representa-
tions occur in the representation of a group, then P j projects onto the sum of the
corresponding subspaces, i. e. the definition (35) now leads to
1
Pj = | j, n n, j| , (48)
g j,n
where the sum j extends only over the representations which are equivalent to each
other. The most important aspect of (48) is that subspaces with a particular, identical
symmetry behaviour are sorted out.
The above proof is also interesting in the sense that we do not at all need to know
the explicit form of | j, n, |k, m or to determine it; only general properties enter the
proof.
6.5 The result can be found in the text of 6.
Chapter 7
in (2) obeys
N
N
H( j)Ψk = EΨk with E= Ek , (4)
j=1 k=1
since
N 4
N
N 4
N
H( j) χkl (l) = χkl (l)H( j)χk j ( j) (5)
j=1 l=1 j=1 l=1
l= j
Chapter 7 51
N 4
N
χkl (l)E k j = EΨk.6) (6)
j=1 l=1
yields
1
Ω=
N!
7 8
4 ∗
× (−1) P+P χk j ( j)V(l, m)χk ( j )dV1 . . . dVN . (8)
j
P(k) P (k ) j, j
Due to
7 8
∗
χ j χk dV = δ jk (9)
the permutations P(k), P (k ) in (8) must be identical up to the factors in which j, j
are the same as l, m, i. e. where
kl = kl
and km = km (10)
or
kl = km
and km = kl . (11)
For (10), the permutations P(k), P (k ) are the same and (−1) P+P = 1, for (11)
they differ by an odd permutation and (−1) P+P = −1. We thus find
1
V(l, m) = (N − 2)! Vkk ,kk − Vkk ,k k (12)
N! k,k
with
7 8
Vij,kl = χi∗ (1)χ ∗j (2)V(1, 2)χk (1)χl (2)dV1 dV2 . (13)
The factor (N − 2)! comes from the number of possible permutations in (8).
Note that the indices on the variable within the integral play no role. For this reason,
to obtain
52 Solutions
1
Ω= V(l, m) (14)
2 l,m
l=m
Ω= Wkk , (16)
k
with
7 8
Wkk = χk∗ (1)W(1)χk (1)dV1 . (17)
7.2 We have
7 8
E= Ψ ∗ HΨdV1 . . . dVN (18)
with
1
H= H( j) + V(l, m) . (19)
j
2 l,m
l=m
with
7 8
Hkk = χk∗ Hχk dV , (21)
and the definition (13). W separate the wavefunction χk into its spatial part ψq and
its spin part sm
χk = ψq · sm (22)
Chapter 7 53
with
sm sm = δmm . (23)
Since the electronic
6 shell
6 is closed, there are just as many spin-↑ as spin-↓
electrons, so that → 2 , but in the case of Vkk ,k k , the spins of k and k are the
k q
same:
E=2 Hq,q + 2Vqq ,qq − Vqq ,q q , (24)
q qq
q=q
where
Vq1 q2 ,q3 q4 = ψq∗1 (1)ψq∗2 (2)V(1, 2)ψq3 (1)ψq4 (2)dV1 dV2 . (25)
2 !
δψ ∗ E − 2 εq
ψq dV = 0 . (27)
q
q
∗ ∗
B) δψq∗ (1) 2 ψq (1)ψq (2)V(1, 2)ψq (1)ψq (2)dV1 dV2
q q
q =q
=4 dV2 ψq (2) 2 V(1, 2)ψq (1) (29)
q
q =q
C) δψq∗ (1) − ψq∗ (1)ψq∗ (2)V(1, 2)ψq (1)ψq (2)dV1 dV2
q q
q =q
= −2 dV2 ψq∗ (2)ψq (2)V(1, 2) ψq (1) (30)
q
q =q
54 Solutions
D) δψq∗ (1) −2 εq | ψq |2 dV = −2εq ψq (1) . (31)
q
2 (A + B + C + D) = 0 .
1
(32)
An iterative solution with a step denoted by i means that we can write (32) in
the form
(H − εq )ψqi+1 (1)+2 |ψqi (2)|2 V(1, 2)dV2 ψqi+1(1)
q =q
∗
− ψqi (2)ψqi (2)V(1, 2)dV2 ψqi+1
(1) = 0 . (33)
q =q
If the (i + 1)-th step again leads to ψqi , then clearly (33) is fulfilled for ψqi+1 = ψqi =
ψ.
7.3 We obtain −13 Ψmn with the aid of
+
an↓ am↑ Ψ , n = m, k . (1)
we not that
a+j↑ a j↓ ak↑
+ + + + +
ak↓ = ak↑ ak↓ a j↑ a j↓ for k = j (4)
and
+ + + + + +
ak↑ ak↓ ak↑ ak↓ = −ak↑ ak↑ ak↓ ak↓ = 0, (5)
as well as
' (
a+j↑ a j↓ an↓
+ +
am↓ = a+j↑ δ jn − an↓+
a j↓ am↓+
' (
= a+j↑ am↓
+
δ jn − a+j↑ an↓
+ +
δm j − am↓ a j↓ . (6)
Chapter 7 55
7.5 To calculate
9 :
Ψk1 Ω Ψk1 (1)
with
Ψk j = ak+j Φ0 , (2)
and
obtaining
9 : 9 :
E k ak+ Φ0 ak+ ak ak+1 Φ0 = E k Φ0 ak1 ak+ ak ak+1 Φ0
1
where
Φ0 | Φ0 = 1 . (9)
The final result for (1) with (2) and (4) is thus
9 :
Ψk1 Ω Ψk1 = E k δkk1 δkk1 . (10)
so that (1) vanishes for (14). The computation of (1) and later also of (9) with (4) or
(14) can e carried out in a much more obvious and efficient manner if we interpret the
effect of the annihilation operator ak in (5) as follows: it can annihilate an electron in
the state k only when it was previously created in the same state from the vacuum Φ0 ,
i. e. we must have k = k1 and it follows that
ak ak+ Φ0 = Φ0 . (16)
Chapter 7 57
ak ak+1 Φ0 = 0 . (17)
Now applying the creation operator ak to (16), we generate the new wavefunction
Ψk = ak+ Φ0 . The bracket in in (5) can now be interpreted as
9 :
ak+ Φ0 ak+ Φ0 ≡ Ψk1 Ψk = δk1 k , (18)
1
which, due to the orthogonality of the wavefunctions is just equal to the Kronecker
delta, as given. The orthogonality can be readily demonstrated from (3), (6), and (7).
Later, we shall explain the procedure for many-particle wavefunctions.
We investigate
9
Ψk1 k2 Ω Ψk1 k2 (19)
for
Using (6), we transfer all the annihilation operators to the right-hand side and
apply (7):
9 :
E k Φ0 ak2 ak1 ak+ ak ak+1 ak+2 Φ0
9 ' ( :
= E k Φ0 ak2 ak1 ak+ δkk1 − ak+1 ak ak+2 Φ0
9 :
= E k Φ0 ak2 ak1 ak+ ak+2 Φ0 δkk1
9 :
− E k Φ0 ak2 ak1 ak+ ak+1 Φ0 δkk2 . (24)
Application of the exchange relations can now be continued. The final result is:
58 Solutions
9 :
E k Φ0 ak2 ak1 ak+ ak ak+1 ak+2 Φ0
= E k (δkk1 δkk1 δk2 k2 − δkk1 δk1 k2 δkk2
− δkk2 δkk1 δk1 k2 + δkk2 δkk2 δk1 k1 ) . (25)
6
For k (13), we find
E k1 + E k2 δk1 k1 δk2 k2 − E k1 + E k2 δk1 k2 δk2 k1 . (26)
The evaluation of (23) and of the following expression (27) can be carried out
much more efficiently (see below). We finally treat
9 :
Ψk1 k2 a+j a+j V j1 j2 ; j1 j2 a j1 a j2 Ψk1 k2 , (27)
1 2
V j1 j2 ; j1 j2 Φ0 | ak2 ak1 a+j a+j a j1 a j2 ak+1 ak+2 |Φ0 . (28)
1 2
Making use of the exchange relations, we transfer all the annihilation operators to
the right-hand side. The somewhat lengthy but elementary computation yields:
9 :
Ψk1 k2 a+j a+j V j1 j2 ; j1 j2 a j1 a j2 Ψk1 k2
1
2
= V j1 j2 ; j1 j2 δk1 j1 δk2 j2 − δ j1 k2 δ j2 k1 δk1 j2 δk2 j1 − δk2 j2 δk1 j1 . (29)
Finally, we introduce the more elegant method for calculating the matrix elements
of many-body functions, which we will explain using the (4) as an example. The
many-body functions have the form
where all the k s are different, since otherwise, due to ak+ ak+ = 0, Ψk1 ...k N would
vanish. Furthermore, due to ak+ ak+ = −ak+ ak+ , we can bring the indices (quantum
numbers) into a particular ordering which we are free to determine, e. g. k1 <
k2 . . . < k N . We consider
9 :
Ψk1 ...kN ak+ ak Ψk1 ...k N
9 :
= ak+ . . . ak+ Φ0 ak+ ak ak+1 ak+2 . . . ak+N Φ0 . (31)
1 N
Applying ak to the right, we remember that only an electron already in the state k
can be annihilated. We thus have k = k j for some j = 1, . . . , N. Otherwise, we
obtain zero. To carry out the “annihilation”, we have to bring ak into the j-th position
in ak+1 . . . .ak+N , i. e. ak must be exchanged ( j − 1) times with ak+l , l < j. Due to (6)
with k = k , this yields a factor of (−1) j−1 . We then transfer the creation operator ak+
in (31) to the now empty position. This again yields a factor of (−1) j−1 . All together,
Chapter 8 59
we thus have
therefore is all that remains of (31). It can readily be proved with the aid of (6) and
(7). The procedure can be applied in an analogous way to
Ω = ak+ ak (35)
4
g
+ + + +
−1 Ψm = ak↓ · am↓ an↓ Φ0 .
3 n
ak↑ (1)
k=1
To evaluate (7.37), we must compute the expectation value of (7.55) with the
corresponding new indices with respect to (1). For the computation of the expectation
values, we can use the fact that the annihilation operators ak+ ↓ or ak+ ↑ act in (1) where
k = k and the spins are the same. Here, however, we must keep in mind the sign
change due to the exchange operations. The final result is given in (7.37).
Chapter 8
∆E · ∆t ≈ h . (1)
Since the ground state has an infinite lifetime, its energy is precisely defined.
The lifetime broadening of a transition line is thus due only to the energy width,
i. e. the uncertainty, of the excited state:
∆E 1
∆ν = = . (2)
hc c · ∆t
60 Solutions
For the energy uncertainties of the two excited states a and b and the linewidths
of their transitions to the ground state, we thus have
a) ∆t = 10 s : ∆E = 6.6 · 10−35 J
ν = 3.3 · 10−12 cm−1
b) ∆t = 1 ns : ∆E = 6.6 · 10−25 J
ν = 3.3 · 10−2 cm−1 .
8.2 The thermal population ratio N2 /N1 of two states with the energies E 1 and E 2
is given in equilibrium by the Boltzmann distribution
N2
= e−∆E/k T (1)
N1
With the value given, N = 105 , one obtains for ∆E = 20.15 cm−1 :
a) T = 29 K : N2 = 2.69 · 104
b) T = 290 K : N2 = 4.75 · 104
c) T = 2900 K : N2 = 4.97 · 104
a) T = 29 K : N2 = 0
b) T = 290 K : N2 = 0
c) T = 2900 K : N2 = 5
Chapter 9
9.1 Only molecules with permanent electric dipole moments exhibit a pure mi-
crowave rotational spectrum: H2 O, H2 O2 , CH3 Cl, CH2 Cl2 , NH3 , NH4 Cl, HCl, HBr.
For molecules such as CH4 and CS2 , rotational spectra become observable only
when IR-active vibrations are excited.
Chapter 9 61
9.2 a) The spectral position ν of the transition between the rotational levels J and
J + 1 is (from (9.15)) given by
The spectral spacing ∆ν between each two neighbouring lines is, in this simpli-
fied model, independent of J:
With the given value ∆ν = 0.71433 cm−1 , one finds for the rotational constant
of Br 19 F:
79
B = 0.357 cm−1
Θ = 7.84 · 10−46 kg m2 .
The moment of inertia of a diatomic molecule with the atomic masses m 1 and m 2
and the bond length (i. e. the internuclear distance) R can be calculated from
where
m1m2
mr = (4)
m1 + m2
denotes the reduced mass in the centre-of-mass system. With (3) and (4), one obtains
from Θ the bond lengths
The transition moment between two rotational levels of a linear molecule depends
to a good approximation only on the electric dipole moment of the molecule and
can therefore be considered to be constant for all purely rotational transitions. The
intensity of a line in a pure rotational spectrum can thus be explained in terms of
the population N J of the absorbing state alone; it in turn is given by the degeneracy
factor g J of the level and its thermal population at the temperature T (Boltzmann
distribution):
NJ g J −(E J −E0 )/kT
= e (5)
N0 g0
62 Solutions
and under the assumption that the bond length is the same for different isotopes, it
follows that
B1 m r,2
= (2)
B2 m r,1
ν = 2B (J + 1) (1)
The transitions J1 and J2 have the same intensity for N J1 = N J2 and therefore
for
N0 (2J1 +1) e−hcB J1 (J1 +1)/kT = N0 (2J2 +1)e−hcB J2 (J2 +1)/kT . (3)
With the values computed above for J1 and J2 , this condition is met at a temper-
ature of
90 hcB
T= . (4)
k ln 73
T = 1620.8 K .
9.5 The spectral position of a line in a purely rotational spectrum of a rigid rotor
can be calculated from (9.15):
have a spacing of 2B ≈ 16.8 cm−1 , which, together with (1), permits the following
identification:
J1 = 4; J2 = 5 ; J3 = 6 ; J4 = 7 .
The model of a rigid rotor is greatly simplified. On replacing it by a nonrigid
rotor, one takes the effect of centrifugal stretching into account and thus obtains for
the energy (in cm−1 ) of a pure rotational state of quantum number J
F(J) = B J(J + 1) − D J 2 (J + 1)2 , (3)
where D is the centrifugal stretching constant; for a diatomic molecule, we have
3
D= (4)
4π k Θ 2 Re2 c
(Θ: moment of inertia of the molecule; Re : equilibrium internuclear distance without
rotation; k: force constant of the elastic valence oscillation along the internuclear
axis). The line belonging to the transition J → J + 1 has the energy
ν J→J+1 = F(J + 1) − F(J) = 2B (J + 1) − 4D (J + 1)3 . (5)
Inserting the corresponding J values for the first two transitions given, ν1 and
ν2 , we obtain the system of linear equations
J1 = 4 → J2 = 5 : ν1 = 10 B − 500 D (6)
J2 = 5 → J3 = 6 : ν2 = 12 B − 864 D (7)
and thus
6ν1 − 5ν2 1
D= and B= ν1 + 50 D . (8)
1320 10
Inserting the numerical values yields
D = 3.70 · 10−4 cm−1 and B = 8.47 cm−1 .
Chapter 9 65
The resulting exact value of B agrees sufficiently well with the value used above,
so that the correspondence of the J values to the lines is confirmed. Making use of
the well-known formula for the rotational constant,
h
B= (9)
8π 2 c m r Re2
and inserting the atomic masses m 1 H = 1.673 ·10−27 kg and m 79 Br = 131.03 ·10−27 kg
as well as
m 1 H m 79 Br
mr = , (10)
m 1 H + m 79 Br
the equilibrium distance between the nuclei and thus the average bond length of the
molecule at rest can be found:
Re = 1.41 · 10−10 m = 1.41 Å .
The model of the nonrigid diatomic rotor is based on the assumption of an elastic
coupling of the nuclei with the force constant k. The resulting harmonic oscillation
along the bond axis has the fundamental frequency
k
ω= . (11)
mr
Solving this equation for k and inserting into (4), and making use of (9) with
some elementary rearrangements, we find for the oscillation frequency
B3
ω = 4π c . (12)
D
With the values of D and B obtained above, this yields
∧
ω = 4.83 · 1014 s−1 = ν = 2564 cm−1 .
9.6 The moment of inertia Θ of the hydrogen cyanide or Prussic acid molecule
H−C≡N in its centre-of-mass system is
Θ = m C RC2 + m N RN
2
+ m H RH
2
. (1)
Here, m C , m N and m H are the relative atomic masses of carbon, nitrogen and
hydrogen, and RC , RN , RH are the distances of each of the atoms from the centre of
mass.
In the centre-of-mass system, we have
m N RN = m C RC + m H RH (2)
so that, with
RCN = RC + RN (3)
66 Solutions
and
RCH = RH − RC (4)
we have three equations at our disposal with which the distances in the centre-of-
mass system in (1) can be eliminated. With the total molecular mass
M = mC + mN + mH , (5)
Θ = 1.885 · 10−46 kg m2
B = 1.485 cm−1 .
Fig. S.20. A linear triatomic molecule HCN: bond lengths and distances from the atoms to
the centre of mass S
L 2x L 2y L 2z
E= + + . (1)
2 Θxx 2 Θ yy 2 Θzz
Chapter 9 67
The ammonia molecule, NH3 , is a symmetric top with an axis of rotation which
in the following is taken to be the z axis of the coordinate system. Then the following
relation holds:
Θzz ≡ Θ . (2)
Owing to the symmetry of NH3 , the two remaining principal components of the
moment of inertia are equal; the associated principal axes are perpendicular to the
rotational axis:
Θxx = Θ yy ≡ Θ⊥ . (3)
L 2x + L 2y L 2z
E= + (4)
2 Θ⊥ 2 Θ
2
L 1 1
= + L 2z − . (5)
2 Θ⊥ 2 Θ 2 Θ⊥
L 2 = 2 J(J + 1) , (6)
and finally
E
F(J, K) = = B J(J + 1) + C K 2 (9)
hc
with the rotational constants
h h 1 1
B= and C = − . (10)
8π 2 c Θ⊥ 8π 2 c Θ Θ⊥
From the data and formulas given, we can compute the two principal elements
of the moment of inertia tensor of the symmetric-top molecule, obtaining
68 Solutions
Θ⊥ = 2.86 · 10−47 kg m2
Θ = 4.38 · 10−47 kg m2
B = 9.78 cm−1
C = −3.39 cm−1 .
Due to Θ > Θ⊥ , we require C < 0, so that in the case of NH3 we are dealing with
a “cushion-shaped” molecule. The rotational spectrum of the molecule is obtained
from (9) taking the selection rules
∆J = ±1, ∆K = 0 (11)
9.8 As derived in problem 9.5 (Eq. 12), the frequency of the valence oscillation of
a diatomic molecule is determined from the rotational constant B and the centrifugal
stretching constant D according to the relation
B3
ω = 4π c . (1)
D
With the values given, we find
∧
ω = 5.64 · 1014 s−1 = ν = 2995 cm−1 .
The experimental value is ν = 2991 cm−1 . The discrepancy results from the
use of an insufficiently precise model as the basis of the calculation: the diatomic
molecule is treated as a harmonic oscillator by approximating the bond as an elastic
spring and applying the linear force relation (Hooke’s Law), F = −k (R− Re ). Mak-
ing use of an anharmonic oscillator potential for the bond leads to an improvement
of the calculated values.
9.9 The reduced mass of 12 C 16 O is 1.139 · 10−26 kg, and the bond length
is 112.82 · 10−12 m. From these values, we can compute the rotational constant
h h
B= = , (1)
8π 2cΘ 8π c m r R2
2
obtaining
B = 1.931 cm−1 .
ν J→J+1 = 2B (J + 1) . (2)
Chapter 9 69
For the first four lines, one obtains from this formula the microwave frequencies:
∧
ν0→1 = 2B = 3.862 cm−1 = 115.86 GHz
∧
ν1→2 = 4B = 7.724 cm−1 = 231.72 GHz
∧
ν2→3 = 6B = 11.586 cm−1 = 347.58 GHz and
∧
ν3→4 = 8B = 15.448 cm−1 = 463.44 GHz .
An analogous calculation leads for the isotopes 13 C 16 O to m r = 1.191 · 10−26 kg
and B = 1.847 cm−1 , and thus to
∧
ν0→1 = 3.694 cm−1 = 110.82 GHz ,
In order to obtain a spectral separation of the two lines belonging to the 0 → 1
transitions, one would need a resolution defined by
ν ν0→1
A= = . (3)
∆ν ν0→1 − ν0→1
With ∆ν = 0.168 cm−1 or ∆ν = 5.04 GHz, this corresponds to a resolution of
A = 23.0 .
Chapter 10
10.1 All molecules whose dipole moment changes during oscillation also absorb
radiation in the infrared spectral region (vibrational absorption spectra). In the case
of symmetric molecules, in particular bending vibrations and asymmetric stretching
vibrations are important, since the symmetric stretch vibrations are IR inactive. Thus
of the molecules given, all exhibit IR absorption with the exception of H2 and N2 .
In the case of the linear azide ion, N−3 , the bending vibration is IR active, as can be
seen from the mesomeric representation:
|N−N≡N| − ←→ N=N=N − ←→ |N≡N−N| − .
Chapter 10 71
10.2 The total number of all the thermodynamic degrees of freedom of an N-atomic
molecule is f = 3N. The balance for translation, rotation, and vibration is as follows:
Number of vibrational
3N − 5 for a linear molecule
degrees of freedom: fV =
3N − 6 otherwise .
From this it follows that the number of vibrational degrees of freedom f V for
a) HBr (linear) : fV =1
b) OCS (linear) : fV =4
c) SO2 (nonlinear) : fV =3
d) H−O−O−H (nonlinear) : fV =6
e) H−C≡C−H (linear) : fV =7
f) C6 H6 : fV = 30 .
From the given values, k = 855 N/m and m r = m Proton = 1.6726 · 10−27 kg,
one obtains
10.4 Since the energy levels of an harmonic oscillator obey the equation
1
E v = ω v + with v = 0, 1, 2, . . . , (1)
2
the minimum excitation energy E min is given by
k
E min = ω = , (2)
mr
b) At the oscillation frequency ν = 5 Hz and ω = 2πν, one finds for the movement
of a mechanical clock the minimum excitation energy
G 0 = 948.5 cm−1 .
one assumes a linear force law and computes the force constant k from
k = m r ω2e . (11)
This maximum vibrational energy can be considered as the lower limit of the
energy continuum, so that after subtracting the zero-point energy, the dissociation
energy D0 of the molecule if found to be:
D0 = G(vmax ) − G 0 (17)
or
kJ
D0 = 63 970 cm−1 = 7.93 eV = 765.3 .
mole
This is not an especially good estimate. Its deviation from the experimental
value
0 = 5.91 eV is due in particular to the neglect of terms of higher order in
D
v + 12 in the expression for the energies. The cubic, quadratic and higher terms
are important especially for large values of v; in the approximation used, we have
namely G(v) → −∞ for v → ∞.
10.6 The given data permit a calculation only in the harmonic oscillator approxi-
mation. For the energy terms, we thus find the expression
1
G v = νe v + , (1)
2
and thus we have for the zero-point energy of the molecule
1
G0 = νe . (2)
2
Under the assumption that the molecule is in its vibrational ground state v = 0
both before and immediately after the reaction, the energy difference ∆E between
the reactants and the products is due solely to their different zero-point energies:
With the given values for the νe of the individual molecules, we obtain
kJ
∆E = 129 cm−1 = 1.54 .
mole
In the reaction of one mole each of reactant molecules, an energy of 1.54 kJ is
thus set free – the reaction is exothermic.
76 Solutions
10.7 The force constant k of a molecular bond can be calculated on the model of
an harmonic oscillator from
k = m r ω2 = 4π 2 c2 m r ν2 . (1)
Here, m r is the reduced mass of the molecule and ν is the frequency of the
fundamental oscillation. For the hydrogen halides, the following table can be written:
1
H 19 F 1
H 35 Cl 1
H 81 Br 1
H 127 I
ν/cm−1 4141.3 2988.9 2649.7 2309.5
m r /10−27 kg 1.598 1.624 1.653 1.661
k/N/m 968.0 515.7 411.7 314.4
10.8 The iodine molecule is treated as an anharmonic oscillator, so that the vibronic
energy terms are given by
1 1 2
G v = νe v+ − xe νe v + . (1)
2 2
From this, we find the spacing ν0→1 of the first two vibrational levels
and with the given values for the vibrational constant νe and the anharmonicity
constant xe
10.9 The diatomic functional groups which contribute are treated as a first approx-
imation as harmonic oscillators. Their vibrational frequency is then
k
ω = 2πc ν = . (1)
mr
The frequency of the O−D stretching vibration can be estimated from the value
for the O−H vibration:
m r,OH
νO–D ≈ νO–H (3)
m r,OD
Since the force constant of the C−S group is comparable at most with that of
the C−O single bond, but not with that of the C=S double bond (different bonding
character), they can be estimated as:
m r,CO
νC–S ≈ νC–O (4)
m r,CS
leading to
νe = 2991.3 cm−1 .
G 0 = 1495.7 cm−1 .
B = 10.59 cm−1 .
For the fundamental oscillation, v = 1 and v = 0, so that Eq. (7) can be
simplified to
ν(J , J ) = νe + B J (J + 1) − J (J + 1) . (8)
Chapter 10 79
d) Two qualitative differences are found between the spectrum calculated in (c)
and the experimentally-determined spectrum.
On the one hand, chlorine is found in nature as an isotopic mixture of 35 Cl and
37
Cl in the ratio 3:1. Due to the different reduced masses of the two isotopically
different HCl molecules, one observes two spectra which are shifted relative to each
other and exhibit an intensity ratio of 3:1.
Secondly, another difference is due to vibrational stretching. It leads to a loss
of validity of the Born-Oppenheimer approximation, since the internuclear distance
now depends on the vibrational state. The rotational constants Bv and Bv are then
different, and the transition energies from (7) are
Since the internuclear distance is greater in the higher state v than in the state
with v , and therefore Bv > Bv , the lines of the P branch shift further apart with
increasing J (i. e. in the direction towards the outside of the vibrational band).
For the R branch (J = J + 1), from (9) we find
Since Bv > Bv , the lines in the R branch move closer together with increasing
J , until they finally reverse along the wavenumber axis and shift towards the centre
of the band. The R branch thus exhibits a sharp edge.
80 Solutions
10.11 The selection rules for the rotational-vibrational transition (v , J , M J ) −→
(v , J , M J ) with M J = −J, . . . , +J are given by
∆v = 0, ±1, ±2, . . .
∆J = ±1
and ∆M J = 0, ±1 .
10.12 As derived in problem (10.10d), the positions of the lines in the R branch
(J = J + 1) of the rotational-vibrational spectrum of a diatomic molecule such as
HCl are found from
With increasing J , the lines move closer together, until finally at JK a direction
reversal along the wavenumber axis occurs. JK is the level which forms the band
edge of the R branch.
The spacing between two neighbouring lines in the R branch with J = JK and
J = JK + 1 is
At the band edge, ∆ν R becomes negative, so that with Bv > Bv , the value of
the rotational quantum number JK can be calculated:
Bv
JK > − 2. (3)
Bv − Bv
Chapter 10 81
JK > 32.46 ⇒ JK = 33 .
Beyond JK + 1 = 34, the line of the R branch move again towards the centre
of the band. The line corresponding to JK forms the band edge. From (1), it follows
for the fundamental vibrational band that
and, with the given value of ν(1, 0), the band edge is at
hcν2e
De = . (3)
4xe νe
With the given values for νe and xe νe , one obtains
De = 15 505 cm−1 .
The parameter a is related to De and the reduced mass m r of the molecule via
mr mr
a = ωe = 2πcνe . (4)
2De 2De
Using the atomic masses MH = 1.008 g/mole and MRb = 85.47 g/mole, one
finds m r = 1.654 · 10−27 kg and thus
B = 3.02 cm−1
and the rotational constant B(R), which depends on the internuclear distance, is
Re2
B(R) = B. (6)
R2
As a result, the rotational energy (in cm−1 ) is given by
1
E rot (R) = B(R) J(J + 1) = B Re2 J(J + 1) · . (7)
R2
The effective potential of the rotating anharmonic oscillator RbH is finally ob-
tained as the sum of a pure Morse potential and the rotational energy:
As the rotational quantum number J increases, the bond is weakened, until it fi-
nally becomes unstable. This phenomenon is based upon the fact that with decreasing
internuclear distance, the rotational energy increases, while for R > Re , the potential
(Morse) energy decreases. Beyond a certain value of J, the effective potential based
on the sum of these two energies no longer has a minimum; cf. Fig. S.21.
Fig. S.21. A graph of the (effective) potential of the anharmonic oscillator RbH vs. internuclear
distance - - - J = 100 ..... J = 40 —- J = 0
Chapter 10 83
A numerical fit of the function G(v) to the given energy values yields as fit
parameters the vibrational constant νe and the anharmonicity constant xe , Figs. S.22
and S.23.
The function G v computed in this way shows clearly that with increasing vi-
brational quantum number v, the spacing between neighbouring levels becomes
smaller.
Fig. S.22. A graph of the energy values G v : measured points and fit curve (fit parameters:
vibrational constant ν e = 2989.74 cm−1 ; anharmonicity constant x e = 0.0174)
The values for νe and xe can just as well be obtained from a plot of the data for
νv→v+1 with a straight-line fit. A purely algebraic solution of the over-determined
system of equations is also readily possible.
The anharmonicity constant xe is related to the distance De between the energy
minimum of the Morse potential and the edge of the continuum as well as the
vibrational constant νe through
ωe hcνe
xe = = . (3)
4De 4De
From this, the dissociation energy D0 can be computed by subtracting the zero-
point energy of the oscillator, G 0 from De :
hcνe
D0 = De − hc G 0 = − hc G 0 ; (4)
4xe
with the values obtained above, we find
b) Since the Morse potential curves of isotopic molecules are to a first approxima-
tion identical, the values of the potential minimum De , the equilibrium internuclear
distance Re , and the force constant k associated with the potential parameter a are
the same for the bond in the deuterated molecule 2 D 35 Cl as those for 1 H 35 Cl. The re-
duced masses of the two isotopic molecules are however different (in the following,
HCl will be denoted by the index 1, and DCl by the index 2):
and with
γ = 0.7172
The heavy isotope thus vibrates more slowly than the light one. The anharmonic-
ity constant is obtained from (3) with De,2 = De,1 , so that
xe,2 ωe,2
= =γ (7)
xe,1 ωe,1
and thus for DCl
xe,2 = 0.0125 .
The heavy isotope remains closer to its equilibrium position during the vibration,
it does not move as far onto the flat portion of the Morse potential as the light isotope;
so it thus experiences less anharmonicity.
The rotational constants B are inversely proportional to the moments of inertia
and, due to the identical equilibrium internuclear distance, also to the reduced masses
of the isotopic molecules:
B2 m1
= = γ2 . (8)
B1 m2
Using the value of B1 given for HCl, we obtain B2 for DCl:
B2 = 5.45 cm−1 .
The rotational structure of the heavier molecule is thus more finely spaced than
that of the light molecule.
c) From (1), for v = 0 we can derive the zero-point energy G 0,2 of the anharmonic
oscillator DCl:
1 1
G 0,2 = νe,2 1 − xe,2 . (9)
2 2
Making use of the values calculated in part (b), we find
The difference of the dissociation energies of the two isotopic molecules can
be used for their laser photochemical separation. An isotopic mixture HCl/DCl is
∧
excited by intense laser light at ca. 41 700 cm−1 = 240 nm; this is possible e. g. with
a frequency-doubled dye laser. Since the energy of the photons lies between the
dissociation energies of the two isotopes, it is sufficient to break the HCl bonds
while the DCl molecule remains stable. With additional separation procedures one
can then sort out the remaining DCl molecules.
86 Solutions
10.15 The SO2 molecule exhibits three normal modes of vibration, which are sim-
ilar to those of the water molecule. Since in both cases the dipole moment of the
molecule undergoes a change, all of the vibrational modes are IR active. In the sym-
metrical vibrational mode ν1 , only the bond lengths change to first approximation,
while the bond angle Θ remains constant. In contrast, in the ν2 mode, mainly the nor-
mal coordinate Θ varies, while the bond lengths change only a little. In polyatomic
molecules, vibrations can change the symmetry of the electronic wavefunction. The
electronic transition dipole moments thus contain coupled electronic/vibronic matrix
elements, and a large value of the vibronic overlap integral leads to intense lines.
In the case of SO2 , the overlap of the “bending oscillation” ν2 with the geometric
variation between the ground and the excited state is greatest (the bond angle Θ
changes and the bond lengths remain constant). The 0−0 transition is thus followed
by an intense vibrational series with line spacing ν2 . Although the other vibrational
modes are also IR active, they are observed with much lower intensities.
Chapter 11
Total momentum:
P= Pi = momenta of the nuclei (3)
i
with
Li = Ri × Pi (4)
and
P2
H= i
+ V = H0 + V . (5)
i
2m i
Chapter 12
12.1 Since the H2 molecule has no permanent electric dipole moment, the pure
rotational spectrum cannot be observed as a microwave absorption spectrum. Instead,
one employs Raman spectroscopy.
The condition for Raman activity of this molecule is a change in its polarisability
on rotation. Since the length of each principal axis i of the polarisability ellipsoid
√
is proportional to 1/ αi (αi : polarisability in the direction i), its sections perpen-
dicular to the molecular axis are circular. The section in the plane containing the
molecular axis is, in contrast, for non-spherically-symmetric molecules always a
non-degenerate ellipse. Upon rotation of the molecule about an axis which is not
the molecular symmetry axis, the polarisability in the plane of polarisation of the
exciting light thus changes, so that the pure rotational spectrum can be observed by
applying Raman spectroscopy.
The rotational states of the molecule are given in first approximation by
FJ = B J(J + 1) . (1)
In the Raman spectrum, the selection rule for optical transitions is ∆J = ±2;
the distance of the lines from the band origin is therefore:
ν J = ν J → J+2 = B (4J + 6) (2)
and the spacing of two neighbouring rotational Raman lines is:
∆ν = ν J+1 − ν J = 4B . (3)
88 Solutions
can be calculated using the atomic mass m H = 1.673 · 10−27 kg, the reduced mass
m r = 12 m H , and the equilibrium bond length Re = 0.7414 Å; the result is
B = 60.829 cm−1 .
∆ν = 243.3 cm−1 .
12.4 The ammonia molecule, NH3 , is a symmetric top, whose symmetry axis
passes through the N atom. The two principal moments of inertia perpendicular and
parallel to the axis of symmetry have the values
leading to B = 9.78 cm−1 and C = −3.39 cm−1 . The positions of the rotational
levels are given by
F(J, K) = B J(J + 1) + C K 2
with K = 0 , ±1 , ±2 , . . . , ±J . (2)
Here, the quantum number J denotes the total angular momentum of the
molecule, while K refers to rotation around the axis of symmetry:
|L | = K . (3)
The rotation around the symmetry axis is not Raman active, since the polaris-
ability of the molecule remains unchanged during this rotation. The first selection
rule for Raman transitions in symmetric-top molecules follows from this:
∆K = 0 . (4)
∆J = 0 , ±1 , ±2 for K = 0 , (5)
∆J = ±2 for K = 0. (6)
In the special case of the symmetric top, we thus observe that for all rotational
states with J = 0, Raman transitions with ∆J = ±1 are allowed. The Raman
spectrum consists of a superposition of the two subspectra with ∆J = ±1 (P and R
branches) and ∆J = ±2 (O and S branches).
If J and J are the rotational levels of the molecule before and after the Raman
scattering process, with ∆J = J − J , then we find from (2), taking the selection
rules (4–6) into account, the pure rotational Raman shift ∆ν = FJ − FJ of the
scattered light relative to the primary light for the Stokes lines:
S branch:
∆J = +2 ⇒ ∆ν = −B (4J + 6) (J = 0, 1, 2, . . . )
R branch:
∆J = +1 ⇒ ∆ν = −2B (J + 1) (J = 1, 2, 3, . . . )
90 Solutions
Anti-Stokes- lines:
O branch:
∆J = −2 ⇒ ∆ν = B (4J − 2) (J = 2, 3, 4, . . . )
P branch:
∆J = −1 ⇒ ∆ν = 2B J (J = 2, 3, 4, . . . ).
∧
The wavelength of the primary light (N2 -Laser) lies at 336.732 nm = 29 697.2
−1
cm . For the innermost Raman lines, we obtain the following positions:
J = 0 1 2 3
Stokes: S branch 29 638.5 cm−1 29 599.4 cm−1 29 560.3 cm−1 29 521.2 cm−1
337.39 nm 337.84 nm 338.29 nm 338.73 nm
R branch 29 658.1 cm−1 29 638.5 cm−1 29 619.0 cm−1
337.17 nm 337.39 nm 337.62 nm
Anti-Stokes: O branch 29 755.9 cm−1 29 795.0 cm−1
336.06 nm 335.62 nm
P branch 29 736.3 cm−1 29 755.9 cm−1
336.28 nm 336.06 nm
12.5 a) IR and Raman lines do not occur together, they are complementary
(cf. problem 12.3). From this we can conclude that the molecule A2 B2 has a centre
of inversion. Since an IR line with PR structure is observed, it must also be a linear
molecule. The general structure formula is thus
A−B−B−A .
H−C≡C−H
as follows:
1)3374 cm−1 ←−→←−→ Raman active symmetric stretching vibration C−H
2)3287 cm−1 ←−→→←− IR active (PR) asymmetric stretching vibration C−H
3)1973 cm−1 ←←→→ Raman active symmetric stretching vibration C≡C
4)729 cm−1 ↑↓↓↑ IR active (PQR) bending vibration
5)612 cm−1 ↑↓↑↓ Raman active bending vibration
(weak)
b) Since one of the vibrations is both IR and also Raman active, the molecule
AB2 cannot have a centre of inversion. Owing to the complex structure of the infrared
bands, it must be a bent molecule:
BB A
A or B B.
Chapter 12 91
Fig. S.24. Rotational Raman spectrum of the symmetric-top molecule NH3 : superposition
of the two series with ∆J = ±1 (above: R and P branch) and ∆J = ±2 (centre: S and
O branch). below: superposed spectrum; every second line of the R and P branches falls
together with a line of the S and O branches. This causes the alternating line intensities
Both structures lead to three vibrational modes. From data on the polarisation
of Raman lines, one obtains information about whether the vibrational mode is
symmetric or asymmetric: in the case of a symmetric molecule, a symmetric vibration
leads to an isotropic deformation of the polarisabiity ellipsoid, so that polarised
primary light remains polarised after Raman scattering. Asymmetrical vibrations
produce an anisotropic deformation of the polarisability ellipsoid with the result that
the molecules are arbitrarily oriented and lead to a depolarisation of the scattered
light.
The two most energetic vibrations lie in the range of the O−H stretching vibra-
tion, so that the observed modes can be attributed to the molecule
92 Solutions
H2 O : (1)
←−
1) 3756 cm−1 − 1 IR active asymmetric stretching
vibration
2) 3652 cm−1 ↑
IR and Raman symmetric stretching
active (polarised) vibration
3) 1595 cm−1 ↑
IR active bending vibration
The frequencies of the bending vibrations are in general lower than those of the
stretching vibrations; also even if they are in principle Raman active, the intensity
of the lines is often so weak that they are not observed.
12.6 Since both molecules have vibrational modes which are both IR and also
Raman active (i. e. the IR and Raman active modes are not complementary), neither
N2 O nor NO2 can have a centre of inversion symmetry. Due to the PR structure of
its IR bands, N2 O must be linear. The only remaining possible structure is thus
N−N−O .
In contrast, the complex rotational structure of the IR bands of NO2 indicate that
this molecule is not linear. On the basis of the available information, we can give
two possible molecular structures:
OO N
N or O O.
12.7 In diatomic homonuclear molecules, the nuclear spin I of the two identical
nuclei A and B (I = I A = I B ) has an influence on the molecular statistics, i. e. on
the probability that a particular molecular state will occur. Under the assumption of
decoupled partial motions, the total wavefunction of the molecule can be written in
terms of a product state:
Ψ(r A , σ A , r B , σ B , ri , σi ) (1)
−1
=Ψ KS
(σ A , σ B ) Ψ ES
(σi )Ψ (R , ri ) R
el
Ψ vib
(R) Ψ (θ, φ)
rot
=Ψ KS
(σ A , σ B ) Ψ (r A , r B , ri , σi )
R
(2)
Since the indices + and − of the term symbol refer to the rotational ground state
J = 0, we have:
for half-integral I:
Iges = 2I , 2I − 2 , . . . , 1 symmetric
Iges = 2I − 1 , 2I − 3 , . . . , 0 antisymmetric.
Each state Iges is (2Iges +1)-fold degenerate; from this fact, one derives the ratio
of the statistical weights of the antisymmetric to the symmetric nuclear spin states
(cf. problem 12.10):
ga I
= . (9)
gs I +1
a) nuclear spin I = 0
Because nuclei with integer spins are Bosons, the total wavefunction Ψ must be
symmetric under exchange of the nuclei, i. e. with (3) and (7):
!
(−1)κ+ = (−1)κ+J+s+π = +1 . (10)
Only the symmetric nuclear spin state Iges = 0 exists, so that
(−1)κ = +1 . (11)
From (10) and (11), it follows that:
!
(−1) = (−1) J+s+π = +1 . (12)
Now with (5) and (6) we have the result
– for even electronic terms (index g):
!
π = 0 ⇒ (−1) J+s = +1
!
⇒ for terms with positive parity (index +): s = 0 ⇒ (−1) J = +1
only rotational states with even J exist.
example: 1 Σg+ , 1 Πg+
⇒ for terms with negative parity (index −):
!
s = 1 ⇒ (−1) J = −1
only rotational states with odd J exist.
example: 1 Σg− , 3 Σg− , 1 Πg−
Chapter 12 95
b) nuclear spin I = 1
The nuclei are again Bosons, so that here also, the total wavefunction must be
symmetric:
!
(−1)κ+ = (−1)κ+J+s+π = +1 . (13)
and in addition, like all the vectors in the space ε( j1 , j2 ), they are eigenvectors of J12
and J22 with the eigenvalues j1 ( j1 + 1) 2 and j2 ( j2 + 1) 2 .
The angular-momentum space ε( j1 , j2 ) can be represented as the direct sum of
invariant subspaces ε(J):
ε( j1 , j2 ) = ε( j1 + j2 ) ⊕ ε( j1 + j2 − 1) ⊕ . . . ⊕ ε(| j1 − j2 |) (3)
The vectors |J, M, which span the subspaces, will be determined in general in
the following.
The subspace ε(J = j1 + j2 )
The ket vector | j1 , j2 ; m 1 = j1 , m 2 = j2 is the only eigenvector belonging to
the eigenvalue M = j1 + j2 and, since J 2 and Jz commute, it is also an eigenvector
of J 2 with the eigenvalue J = j1 + j2 . With a suitable choice of the phase factor,
we then have
| J = j1 + j2 , M = j1 + j2 = | j1 , j2 ; m 1 = j1 , m 2 = j2 . (4)
| j1 + j2 , j1 + j2 − 1
1
= √ J− | j1 + j2 , j1 + j2 (7)
2( j1 + j2 )
1
= √ (J1 − + J2 − ) | j1 , j2 ; j1 , j2 (8)
2( j1 + j2 )
1 2 %
= √ 2 j1 | j1 , j2 ; j1 − 1 , j2
2( j1 + j2 )
% 3
+ 2 j2 | j1 , j2 ; j1 , j2 − 1 (9)
and thus
j1
| j1 + j2 , j1 + j2 − 1 = | j1 , j2 ; j1 − 1 , j2
j1 + j2
j2
+ | j1 , j2 ; j1 , j2 − 1 . (10)
j1 + j2
Chapter 12 97
This vector, which is already normalised, is a linear combination of the two basis
vectors of ε( j1 , j2 ) which belong to M = j1 + j2 − 1. By repeated application of
the operator J− , we obtain the vectors of the subspace up to
|J = j1 + j2 , M = −( j1 + j2 ) = | j1 , j2 ; − j1 , − j2 . (11)
| j1 + j2 − 1 , j1 + j2 − 1 = α | j1 , j2 ; j1 , j2 − 1
+ β | j1 , j2 ; j1 − 1 , j2 . (12)
With a suitable choice of the phase factors, we obtain from (13) and (14) the
relations
j1
| j1 + j2 − 1 , j1 + j2 − 1 = | j1 , j2 ; j1 , j2 − 1
j1 + j2
j2
− | j1 , j2 ; j1 − 1 , j2 . (15)
j1 + j2
a) The above formalism, developed for the general case, will now be applied
to the special case of two nuclear spins j1 = I A = 1 and j2 = I B = 1. The total
nuclear spin I = I A + I B of the molecule can take on the values
I = 2, 1, 0. (16)
The angular-momentum space ε(1, 1) is thus decomposed into the subspaces ε(I =
2), ε(I = 1), and ε(I = 0) with dimensions 5, 3 and 1.
The subspace ε(I = 2)
According to (4), the vector |J = 2 , M = 2 can be written as
|2, 2 = |1, 1; 1, 1 . (17)
Application of the ladder operator J− leads –analogously to (10)– to
1
|2, 1 = √ [ |1, 1; 1, 0 + |1, 1; 0, 1 ] . (18)
2
Furthermore, one finds
1
|2, 0 = √ [ |1, 1; 1, −1+ 2 |1, 1; 0, 0+ |1, 1; −1, 1] (19)
6
1
|2, −1 = √ [ |1, 1; 0, −1 + |1, 1; −1, 0 ] (20)
2
|2, −2 = |1, 1; −1, −1 (21)
The subspace ε(I = 1)
The general result (15) now corresponds to
1
|1, 1 = √ [ |1, 1; 1, 0 − |1, 1; 0, 1 ] (22)
2
and therefore
1
|1, 0 = √ [ |1, 1; −1, 1 − |1, 1; 1, −1 ] , (23)
2
1
|1, −1 = √ [ |1, 1; 0, −1 − |1, 1; −1, 0 ] . (24)
2
It is notable that the vector |0, 1 contains no contribution from the components
|1, 1; 0, 0. The corresponding Clebsch-Gordan coefficient is 0.
The subspace ε(I = 0)
The choice of suitable real phase factors leads to the basis vector of the one-
dimensional subspace:
1
|0, 0 = √ [ |1, 1; 1, −1 − |1, 1; 0, 0 + |1, 1; −1, 1 ] . (25)
3
b) One can derive from the results of (a) the fact that the states belonging to I = 2
and I = 0, |J, M, are symmetric on nuclear exchange, while the states belonging
to I = 1 change their sign on nuclear exchange, and are thus antisymmetric.
Chapter 12 99
12.9 The (unstable) isotope 19 F is a Fermion due to its nuclear spin of 1/2; the total
wavefunction of the molecule 19 F2 is thus antisymmetric under nuclear exchange.
With the notation from problem 12.7, this yields
!
(−1)κ+J+s+π = −1 . (1)
The electronic term for the ground state is even (π = 0) and has positive parity
(s = 0). From this, one can conclude that
!
(−1)κ+J = −1 . (2)
The maximum total spin I which can result from vector addition of the two
nuclear spins I A = I B = 12 is I = 1 (ortho fluorine). The three degenerate states
with M = 0 , ±1 are symmetric (κ = 0), so that due to (2), only rotational states of
odd quantum number J can occur.
In contrast, the state belonging to a total spin of I = 0 (para fluorine) is anti-
symmetric (κ = 1), and its rotational states have even values of J.
The statistical weights of the two types of molecule behave as
gPara ga 1
= = . (3)
gOrtho gs 3
12.10 In order to derive the ratio of the statistical weights of the antisymmetric
and the symmetric states of a diatomic homonuclear molecule in general, we need
to investigate the following cases for the nuclear spins I A = I B = I and the total
spin Iges :
• integer I:
– symmetric states:
Iges = 2I , 2I − 2 , . . . , 0 (I + 1 states)
degree of degeneracy in each case 2Iges + 1
overall abundance:
gs = (2 · 2I + 1) + [2 · (2I − 2) + 1] + . . . + 1 (1)
I
=4 n + I +1 (2)
n=0
= (I + 1) (2I + 1) ; (3)
– antisymmetric states:
Iges = 2I − 1 , 2I − 3 , . . . , 1 (I states)
degree of degeneracy in each case 2Iges + 1
overall abundance:
100 Solutions
ga = [2 · (2I − 1) + 1] + [2 · (2I − 3) + 1]
+ . . . + (2 · 1 + 1) (4)
I−1
=4 n + 3I (5)
n=0
= I (2I + 1) . (6)
• half-integer I:
– symmetric states:
Iges = 2I , 2I − 2 , . . . , 1 (I + 12 states)
degree of degeneracy in each case 2Iges + 1
overall abundance:
gs = (2 · 2I + 1) + [2 · (2I − 2) + 1]
+ . . . + (2 · 1 + 1) (7)
I
5
=4 n +I+ (8)
2
n= 12
= (I + 1) (2I + 1) ; (9)
– antisymmetric states:
Iges = 2I − 1 , 2I − 3 , . . . , 0 (I + 12 states)
degree of degeneracy in each case 2Iges + 1
overall abundance:
Chapter 13
13.1 The information contained in the term symbols of the form 2S+1
Λ±
(g,u) Ω is
collected in the table below. There, we find for a diatomic molecule
– Λ, the z-component of the total angular momentum of all the electrons in the
molecule (the z direction is the direction of the molecular symmetry axis);
– S, the total spin of the shell electrons (2S + 1: multiplicity; z-component: Σ);
– Ω = | Λ + Σ |, the total angular momentum of the electronic shell in the z
direction;
– σ, the symmetry of the electronic wavefunction on reflection in a plane containing
the nuclei;
– P, the parity of the electronic wavefunction of a homonuclear molecule (with
identical nuclear charges and therefore an inversion-symmetric nuclear field),
i. e. the symmetry on inversion of all the particles (gerade/ungerade ≡ even/odd)
(see the table below).
13.2 From the data given, one can extract the following information about the
states of the separated atoms A and B:
A: 1s ⇒ L A = 0 ; m L,A = 0 ;
S A = 12 ; m S,A = ± 21 ;
B: 1s2 2s2 2 p; 1s2 and 2s2 are closed shells with S = L = 0
⇒ L B = 1 ; m L,B = 0, ±1 ;
S B = 12 ; m S,A = ± 12 .
Since AB is a heteronuclear molecule, the possible exclusion of terms due to the
Pauli principle need not be considered. For the molecule AB we thus find:
AB:m L = 0, ±1 ⇒ Λ = 0, 1
⇒ one Σ and one Π term ; S = 0, 1 ⇒ Σ = 0, ±1 .
From this we find the possible terms
Λ = 0: 1
Σ0+ , 1 Σ0− , 3 Σ0+ , 3 Σ0− , 3 Σ1+ , 3 Σ1−
Λ = 1: 1
Π1 , 3 Π0 , 3 Π1 , 3 Π2 .
Λ S Ω Σ σ P Remark
1
Σ+ 0 0 0 0 + 1
Σ + and 1 Σ − not degenerate!
1 +
Σu 0 0 0 0 + u identical nuclear charges; molecular or-
bitals ug
3 +
3
Φ3 3 1 3 0 Φ3 and 3 Φ3− degenerate
3
Φ3− 3 1 3 0 −
3 −
Φg3 3 1 3 0 − g identical nuclear charges; molecular or-
bitals gg or uu
102 Solutions
O+ 2 ∗ 2 2 ∗ 2 4 2 ∗
2 : (σg 1s) (σu 1s) (σg 2s) (σu 2s) (πu 2 p) (σg 2 p) (πg 2 p)
O2 : (σg 1s)2 (σu∗ 1s)2 (σg 2s)2 (σu∗ 2s)2 (πu 2 p)4 (σg 2 p)2 (πg∗ 2 p)2
O− ∗ 2 2 ∗ 2 4 2 ∗
2 : (σg 1s) (σu 1s) (σg 2s) (σu 2s) (πu 2 p) (σg 2 p) (πg 2 p)
2 3
∗ ∗ ∗
2 : (σg 1s) (σu 1s) (σg 2s) (σu 2s) (πu 2 p) (σg 2 p) (πg 2 p)
O2− 2 2 2 2 4 2 4
b) From the electron configurations in (a), the term symbols 2S+1 Λ± (g,u) Ω of
the ground states can be derived. The problem can be simplified by remembering
that closed electronic shells have neither orbital angular momentum nor spin. For
computing the total orbital angular momentum Λ = L z and spin S of the electronic
shells therefore only the outermost unfilled shell needs to be considered.
The homonuclear diatomic molecules have a nuclear field with inversion sym-
metry, so that the electron terms exhibit an even/odd symmetry; with an even number
of electrons in u orbitals, one has a g term, with an odd number, a u term.
O+
2 : Λ = 1 ; S = 12 ⇒ 2 Πg
O2 : Λ = 0 ; S = 0 ⇒ 1Σg+
Λ = 0 ; S = 1 ⇒ 3 Σg−
Λ = 2 ; S = 0 ⇒ 1 ∆g
Λ = 2 ; S = 2 Pauli forbidden
according to Hund’s rule, the state of highest multiplicity lies energetically
lowest; the ground state is thus 3 Σg−
−
O2 : Λ = 1 ; S = 12 ⇒ 2 Πg (π 3 behaves like π 1 )
O2−
2 : all shells are closed, therefore no orbital angular momentum or spin; com-
pletely symmetric state ⇒ 1 Σg+
c) The energetically lowest allowed transition of O2 changes the electronic
configuration of the molecule according to
(σg 1s)2 (σu∗ 1s)2 (σg 2s)2 (σu∗ 2s)2 (πu 2 p)4 (σg 2 p)2 (πg∗ 2 p)2
−→ . . . (πu 2 p)3 (σg 2 p)2 (πg∗ 2 p)3
Here, we have taken the selection rules for radiative transitions, namely ∆Λ =
0 , ±1, ∆S = 0 and in particular also g ↔ u into account. We are thus dealing with
a π → π ∗ transition.
Chapter 14 103
13.4 From the term symbol 3 Πu , one can conclude that we are dealing with S + 1
(triplet state) and Λ = 1. In order to yield an H atom in its ground state upon
dissociation, an electron must occupy the molecular orbital (1sσg ); due to Λ = 1,
the other orbital must then be a π state. Since the molecular state is stable in
comparison to the dissociation products, we can assume that both electrons occupy
bonding orbitals. The odd electron term requires finally one g and one u state for the
participating electrons.
The energetically lowest electronic configuration which fulfills the conditions
listed above is then
(1sσg ) (2 pπu ) .
Chapter 14
14.1 a) For the position G v of the vibronic levels above the minimum of the
potential curve of the given electronic state, the following approximate formula
holds:
1 1 2
G v = νe v + − xe νe v + . (1)
2 2
The spacing between two neighbouring vibrational levels v and v + 1 is then
With (2), this yields the relation between the position of the point of convergence
vC and the anharmonicity constant xe :
1
vC = − 1. (4)
2xe
From this relation, we can compute the points of convergence of the limiting
continuum and thus the number of vibrational levels up to the particular dissociation
limit, namely vC for the ground state and vC for the excited state, with the result
D0 = G vC − G 0 . (5)
One calculates D0 for the ground state and D0 for the excited state:
104 Solutions
kJ
D0 = 56 896 cm−1 = 1.13 · 10−18 J = 680.6 = 7.1 eV,
mole
kJ
D0 = 47 755 cm−1 = 9.49 · 10−19 J = 571.3 = 5.9 eV .
mole
b) The dissociation energies of the ground state and of the electronically excited
state can also be found from spectroscopic data. To this end, we require knowledge
of
– the energy hc ν00 of the 0−0 transition line (from the v = 0 level of the ground
state into the same level of the excited state),
– the energy νC of the point of convergence (distance of the dissociation limit of
the excited state from the v = 0 level of the ground state; the absorption begins
at the latter)
– and the sum of the excitation energies E At of the atomic dissociation products
of the electronically excited state (the difference between the continuum edges
of the ground state and the excited state).
We then find for the dissociation energy D0 of the ground state:
D0 = hc ν C − E At
⇒ D0 = 28 923 cm−1 = 5.75 · 10−19 J
kJ
= 346.0 = 3.6 eV
mole
and for the dissociation energy D0 of the excited state
D0 = hc νC − hc ν00
⇒ D0 = 19 853 cm−1 = 3.94 · 10−19 J
kJ
= 237.5 = 2.5 eV .
mole
Fig. S.25. Visualisation of the calculation of the dissociation energies (explained in the text)
Chapter 14 105
The discrepancy between the results in (a) and in (b) is due to the linear extrap-
olation according to (2) which is employed in (a): the linear relation between ∆νv
and v is extrapolated to vC with ∆νvC = 0. This approximation however becomes
worse and worse as the vibrational quantum number v increases, since for large
values of v in the calculation of the level energies from (1), terms of third and fourth
order in v become significant. This results in a value of vC calculated from (3) which
is larger than the true value and thus an overestimate of the number of vibrational
levels below the point of convergence.
14.2 The energy spacings ∆νv between neighbouring vibrational levels v and v +1
are, according to Eq. (2) in problem 14.1, given by
In the plot of ∆E = ˆ ∆νv against v, one however finds a strong deviation from
the linear behaviour for large values of the quantum number v, so that the linear
extrapolation from small v to the point of convergence vC with ∆νvC = 0, the so
called Birge-Sponer extrapolation, no longer seems reasonable. The function ∆νv (v)
decreases faster than the extrapolation line; cf. Fig. S.26. The reason for this is the
increasing contribution of the terms of third and fourth order in the equation for the
energetic positions of the vibronic levels for increasing v:
1 1 2 1 3
G v = νe v + − xe νe v + + ye νe v +
2 2 2
4
1
− z e νe v + + ... . (2)
2
Extrapolation of ∆νv (v) using a power series of third or fourth order thus leads
to a better result for vC than the linear Birge-Sponer extrapolation.
The dissociation energy D is obtained as the area under the function ∆νv (v),
i. e. the integral
Fig. S.26. A Birge-Sponer plot for determining the point of convergence of the limiting
continuum of I2 (extrapolation to ∆E = 0: vC = 97)
106 Solutions
vC
D= ∆νv (v) dv . (3)
0
Applying this procedure with the given data to the molecule I2 leads to the point
of convergence vC = 97 and the dissociation energy
kJ
D = 12 293 cm−1 = 2.44 · 10−19 J = 147.1 = 1.5 eV .
mole
14.3 a) The given data for the energetic positions of the vibronic levels of the
electronically-excited state of O2 can be evaluated in terms of a Birge-Sponer plot,
cf. Fig. S.27. From the nonlinear extrapolation of the function ∆νv (v) out to the point
of convergence of the limiting continuum vC with ∆νvC = 0, one obtains vC = 18
and, from the area under the curve, the dissociation energy D0 of the excited state
kJ
D0 = 6897 cm−1 = 1.37 · 10−19 J = 82.5 = 0.86 eV .
mole
Fig. S.27. A Birge-Sponer plot for determining the point of convergence of the limiting
continuum of O2 (Extrapolation to ∆E = 0: vC = 18)
b) From the energy ν00 of the 0−0 transition, the dissociation energy D0 of the
excited state, and the total excitation energy E At of the atomic dissociation products,
we can calculate the dissociation energy D0 of the ground state:
D0 = hc ν 00 + D0 − E At
= (50 062.6 + 6897 − 15875) cm−1
⇒ D0 = 41 085 cm−1 = 8.16 · 10−19 J
kJ
= 491.5 = 5.1 eV .
mole
Chapter 14 107
14.4 a) The data given for the oscillation frequency νe of the CO molecule in its
ground stand and the band intervals νe of the vibrational states in the electronically
excited state permit us –within the harmonic-oscillator model– to calculate the force
constants k and k of the molecular bonding in the ground state and in the excited
state:
Due to B < B , we therefore find Re > Re , i. e. the average internuclear
distance is larger in the excited state than in the ground state. Calculation with the
given data yields
Re = 1.13 Å ,
Re = 1.24 Å .
For radiative electronic transitions between different rotational levels, the selec-
tion rule ∆J = 0 , ±1 applies. In a diatomic molecule, the angular momentum of
the electronic shells Ω and the angular momentum N of the rotational motion of the
whole molecule are coupled to the total angular momentum J:
J = N+Ω. (3)
This means that the rotational level J = 0 is lacking in the excited state, while
it exists in the excited state. We can therefore assume that we are dealing with a
transition of the type 1 Σ −→ 1 Π.
b) With the information obtained in part (a), a simplified term scheme can
be sketched, if one retains the harmonic-oscillator approximation and thus draws
parabolic potential curves U(R):
k
U(r) = (R − Re )2 . (4)
2
This term scheme contains the ground state and the excited electronic state
including its vibronic levels. According to the Frank-Condon principle, only vertical
transitions are allowed, since in the adiabatic approximation the internuclear distance
remains constant during the transition.
The absorption begins in the J = 0 level of the ground state for which the prob-
ability density at the equilibrium internuclear distance Re it greatest. The transition
ends at the “turning point” of the J = 1 level of the excited state. Since the greatest
probability density of this state lies in the neighbourhood of the turning point, the
overlap integral of the wavefunctions in the ground state and the excited state is
maximal for the 0–1 transition. For this transition, we can thus expect the highest
intensity.
The equilibrium internuclear distance Re in the excited state is further away from
Re than the turning point of the vibronic levels J = 2, 3, . . . . The intensity of the
0–0 transition should therefore be less than that of the first three or four lines of the
vibrational series.
c) The molecule CO is isoelectronic with N2 , in its ground state it thus has the
same electron configuration:
(σ1 s)2 (σ ∗ 1s)2 (σ2s)2 (σ ∗ 2s)2 (π2 p)4 (σ2 p)2 −→ 1
Σ.
Chapter 14 109
This verifies the assumption derived in (a) for the term symbols of the two states.
14.5 The continuous or diffuse spectra of polyatomic molecules in the short wave-
length region, λ < 200 nm (VUV) have several causes:
– owing to the numerous possibilities of absorption by different chromophore
groups, several band systems overlap;
– the energy is not sufficient to excite the molecule into the dissociation continuum,
whereby large molecules often have flatter potential curves than smaller ones
and are thus less stable;
– in the region of the excitation spectra considered, there is an intersection of
the potential curves of several different electronic terms and thus a tendency to
predissociation, which causes a shorter lifetime and therefore a greater linewidth
in the excited states.
14.6 The molecular orbital which is delocalised over the whole polyene can be
modeled in terms of a potential well of length L = 10 Å with infinitely high walls.
The energy of an electron in this potential well is then quantised according to
n2 h2
En = with n = 1, 2, 3, . . . (1)
8 me L 2
(m e : electron mass). The spacings between neighbouring energy levels become
greater as n increases. Each state which is associated with the quantum number n is
described by the wavefunction ψn :
' nπx (
2
ψn = sin . (2)
L L
The minimum excitation energy of the electron which is in the ground state
n = 1 is, from (1)
h2
∆E min = E 2 − E 1 = 3 , (3)
8m e L 2
and, with the given data,
The minimum excitation energy of the electron lies in the near infrared.
The probability density is given by the squared magnitude of the wavefunction ψ.
The occupation probability W0≤x≤l of the particle in the state n in the range 0 to l is
calculated by integration:
110 Solutions
l l ' nπx (2
2
W0≤x≤l = ψn ψn∗ dx = sin dx (4)
0 L 0 L
l 1 2nπl
= − sin . (5)
L 2nπ L
W0≤x≤l = 0.05 .
Chapter 15
OD = − log T , (4)
and, with the given value T = 16% = 0.16 for λ = 256 nm,
OD (256) = 0.796 .
For a sample thickness of 0.1 cm, we calculate using (2) that the transmission is
T = 83% .
A = c εmax ∆ν . (13)
112 Solutions
With the data given in the problem, one finds the integral absorption of the band
to be
l cm2
A = 1.91 · 1016 = 1.91 · 1016 .
mole cm s mmole s
The oscillator strength f of the transition is found from the value of A thus
calculated by applying the simple relation
f = 2.75 · 10−3 .
8π 2 m e ν
f = |Θmn |2 (7)
3 h e2
and with (5) and (6)
2
32 m e ν L 2 1
a) n → m = n + 1 : f a = − 1 (8)
3π 2 h (2n + 1)2
b) n → m = n + 2 : f b = 0 . (9)
h2
a) n → m = n + 1 : ∆E a = hν = (2n + 1) , (10)
8m e L 2
h2
b) n → m = n + 2 : ∆E b = hν = (n + 1) . (11)
2m e L 2
Inserting into (8) and (9), this gives finally the oscillator strengths of the two
transitions
64 n 2 (n + 1)2
a) n → m = n + 1 : f a = · , (12)
3π 2 (2n + 1)3
b) n → m = n + 2 : f b = 0 . (13)
over 22 C atoms. With an average bond length of R = 140 pm, the length L of the
potential well is then
The levels in the potential well are to be filled with the 22 delocalised π electrons
from the eleven double bonds from the lowest upwards, so that up to n = 11, all the
levels are occupied with two electrons, each with antiparallel spins. The excitation
of the molecule thus starts from the state n = 11. According to (10) and (11), we
can now calculate the excitation energies:
h2
a) n → m = n + 1 : ∆E a = · 23
8m e L 2
∧
= 1,46 · 10−19 J = 7353 cm−1 , (15)
2
h
b) n → m = n + 2 : ∆E b = · 12
2m e L 2
∧
= 3.05 · 10−19 J = 15 346 cm−1 . (16)
These results correctly describe the order of magnitude of the measured transition
energies. Finally, using (12), the oscillator strength of the transition 11 → 12 can be
determined:
f a = 3.1
The oscillator strength gives the ratio between the actual intensity of the transition
and that of an ideal harmonic oscillator. This follows from its definition: for an
electron which is harmonically oscillating in three dimensions, we find f = 1; in
the one-dimensional case, we have f = 13 . The above calculated value of f = 3.1
can thus not be particularly precise. To be sure, we should not expect it to be, since
we are comparing two essentially different models (potential well and harmonic
oscillator).
15.4 a) On cooling of the H2 gas, the populations of the excited rotational and
vibronic states is reduced. The ratio of the population numbers N1 of the first excited
state of energy E 1 and N0 in the ground state is, for a given temperature T , given by:
N1 g1 −E1 /kT
= e (1)
N0 g0
(g1 , g0 : degree of degeneracy of the excited and the ground states; k: Boltzmann’s
constant). As a first criterion for the freezing out of the rotational and vibronic
degrees of freedom, we can apply the condition
!
1st criterion: E 1 = kT . (2)
The population of the first excited state is then (neglecting the different degrees of
degeneracy)
Chapter 15 115
1
N1 = · N0 ≈ 0.37 · N0 . (3)
e
Freezing out of the vibrational degree of freedom thus occurs at the temperature
hc ν0→1
TS,1 = , (4)
k
where ν0→1 = 4159.2 cm−1 is the wavenumber of the first vibrational transition of
hydrogen in its ground state:
TS,1 = 5987 K .
With the rotational constant B = 60.8 cm−1 of the H2 ground state, the temper-
ature for freezing out of the rotational degrees of freedom follows:
hcB J(J + 1) 2hcB
TR,1 = = (5)
k k
with J = 1 for the first excited rotational level and thus
TR,1 = 175 K .
As the second criterion for freezing out of the rotational and vibrational degrees
of freedom, we now require that the population of the corresponding first excited
state decrease to 1% of the population of th ground state:
N1 !
2nd criterion: = 1% = 0.01 . (6)
N0
For the vibrational states, the two degrees of degeneracy are g1 = g0 = 1, so
that with (1), we find
hc ν0→1
TS,2 = . (7)
k ln 100
At a temperature TS,2 , the n = 1 vibrational state is practically unoccupied:
TS,2 = 1300 K .
TR,2 = 30.7 K .
116 Solutions
b) For HCl, we use B = 10.39 cm−1 and ν0→1 = 2885.6 cm−1 . From (4), (5),
(7), and (8) we can then compute the temperatures at which, according to the above
criteria, the rotational and vibrational degrees of freedom of HCl gas freeze out:
TS,1 = 4154 K ,
TS,2 = 902 K ,
TR,1 = 29.9 K ,
TR,2 = 5.2 K .
c) Hydrogen gas can be cooled with liquid helium in a cryostat, since it does not
yet condense at the calculated temperatures.
In contrast, HCl is already solid at the temperatures which are necessary to freeze
out the rotational degrees of freedom (TF = 158.3 K). The effective temperature
for rotation and vibration can however be reduced to the required value in a jet
(supersonic beam).
15.5 The relativistic red shift of the light emitted by the star if it is moving away
from the terrestrial observer at the velocity v F , is given by
λvF c + vF
= . (1)
λ0 c − vF
Here, λvF and λ0 are the wavelengths of the light with and without the Doppler
shift, and c is the velocity of light in vacuum. From this, we obtain the proper velocity
of the star:
λ2vF − λ20
vF = c · , (2)
λ2vF + λ20
where N and N0 are the numbers of ions which are moving with the velocities v
or 0 relative to the observer, and m is the mass of the ions. The full width at half
maximum (FWHM), ∆v, of the velocity distribution is
2kT ln 2
∆v = 2 . (4)
m
Chapter 15 117
Since the velocity v of the ions is much smaller than the velocity of light
c, the Doppler-shifted frequency νv of a moving atom can be determined non-
relativistically from the unshifted frequency ν0 of an ion at rest:
' v(
νv = ν0 1 − . (5)
c
For the wavelength shift of the moving source relative to that of the source at
rest, we find from this the relation
v
δλ = λ0 . (6)
c
The Doppler shift of the radiation emitted by the moving ions is proportional
to their velocity. We thus find from the Gaussian distribution of the velocities a
Gaussian absorption profile which, owing to 4) and (6), has a linewidth (FWHM) of
λ0 2λ0 2kT ln 2
∆λ = ∆v = . (7)
c c m
For a given width ∆λ of the spectral line, one can extract the temperature:
2
c ∆λ m
T= . (8)
2λ0 2k ln 2
T = 8.4 · 105 K .
15.6 The energy uncertainty ∆E of a state with the lifetime τ is given by the
uncertainty relation
∆E · τ ≈ . (1)
Since the ground state has an infinitely long lifetime, its energy is arbitrarily
sharp. The lifetime broadening of an absorption line from the ground state into an
excited state is therefore determined only by the uncertainty of the excited state; it
is inversely proportional to its lifetime.
a) Due to the depopulation of the S2 state through rapid radiationless processes
(internal conversion, vibrational relaxation), its lifetime is of the order of 10−12 s,
while that of the S1 state lies near 10−8 s. Since the S1 state is thus sharper than the
S2 state, the S0 − S1 absorption line is narrower than the S0 − S2 line.
b) Radiative transitions from the triplet state T1 into the ground state S0 are forbid-
den, so that the T1 state is metastable and exhibits a long lifetime τ = 10−8 − 102 s.
The S0 –T1 line is thus in general very narrow.
118 Solutions
Fig. S.28. The photoelectron spectrum of CO after excitation at 21.21 eV. For problem 15.7
E ion = E He − E kin .
The νe values calculated from the vibronic maxima of the bands correspond
approximately to the vibrational constants in the corresponding excited states of
CO+ . For the ground state of neutral CO, one finds νe = 2143 cm−1 . Removing a
2 p π electron weakens the bond, so that the vibrational frequency decreases. 2 p π
can thus be identified as a bonding orbital, 2s σ ∗ in contrast as an antibonding orbital.
Chapter 18 119
15.8 From the spacings of the vibronic maxima in the 9 eV band of the photoelec-
tron spectrum of H2 O, the vibrational constant νe of the corresponding molecular
orbital can be determined:
This value is comparable with the vibrational constant ν1 = 3657 cm−1 of the
symmetric stretching vibration of neutral H2 O. For the 7 eV band, one calculates a
value according to
which is more strongly shifted compared to ν2 = 1595 cm−1 for the bending vibra-
tion. This suggests that the 7 eV electron originates from a more strongly bonding
orbital, since its excitation has a stronger effect on the vibrational behaviour of the
molecule.
Chapter 18
µ= γ I, (1)
ΩL = −γ B . (8)
Thus in a static magnetic field, µ and –from (1)– also the nuclear spins I carry
out a precessional motion around the direction of the field at the frequency ΩL .
b) The gyromagnetic ratio γ for a particular nucleus can be computed from the
corresponding nuclear g-factor g I (5.58569 for 1 H), the nuclear magneton µN =
0.505 · 10−26 A m2 , and Planck’s constant according to
g I µN
γ = . (9)
For the Larmor frequency νL = 1
2π ΩL it follows using (8) that
g I µN
νL = B, (10)
h
and, with the given value for the Earth’s magnetic field B,
νL = 553.4 Hz .
18.2 a) Inserting the fixed magnetic field B = 2.166 T into expression (10) from
problem 18.1 for the Larmor frequency of a proton, one finds
This is, however, the frequency of the radio station SDR 3, which broadcasts from
the Stuttgart Television Tower at high power. The student is worried that therefore
his measurements will be disturbed by the radio signals (or that reception of SDR3
in the laboratory will be disturbed by the NMR apparatus).
b) Solving Eq. (10) from problem 18.1 for the magnetic field B, we find
hν
B= . (1)
µN g I
Chapter 18 121
With the g-factor g I = 5.58569 for protons, 1 H, and the given frequency ν, we
calculate the field strength
BH = 0.71 T .
BC = 2.83 T .
18.3 Denoting the resonance magnetic field for the standard, TMS, as BT and the
resonance magnetic field for the sample substance as BS , the chemical shift δ obeys
the equation
BT − BS
δ = 106 . (1)
BT
There is thus a linear relationship between δ and the field BS , so that the calcu-
lation of the centre of gravity of the lines of a multiplet can be carried out equally
well on the B axis or on the δ axis:
1
B = (B + BS ) (2)
2 S
1
or δ = (δ + δ ) (3)
2
(for a doublet of lines). The chemical shift of the nuclei A and B is defined as the
centre of gravity of the doublets, since in the special case of weak coupling J # δ,
the splitting due to the dipole-dipole interaction is symmetric around the position of
the unsplit line:
(the assignment of the nuclei A and B is arbitrary). The doublet splitting of the two
lines is caused by the dipole-dipole coupling between two nuclei with spins 12 and
the coupling constant J AB . It corresponds to the line spacing in the two doublets:
J AB = 0.1 ppm .
J AB = 10 Hz .
or, more precisely: δ(O−CH3 ) ≈ 3.3 ppm, δ(N−CH3 ) ≈ 2.3 ppm and δ(C−CH3 ) ≈
0.9 ppm.
18.5 For the NMR spectrum of the fluorine nucleus, the coupling constants JHH
between the protons are irrelevant when, as in the present case, the chemical shifts
δ of the three inequivalent protons are very different: ∆δ JHi H j (the protons are
so to speak “very inequivalent”). The dipole-dipole interaction of the F nucleus with
the proton Ha then causes a doublet splitting of the F resonance line with a line
spacing of JHa F ; the interaction with Hb gives rise to an additional splitting of both
lines into pairs with a spacing of JHb F ; and finally, the interaction with Hc causes a
splitting of each line into two new lines at a spacing of JHc F . The final result is a
splitting into 23 = 8 lines of equal intensity.
Chapter 18 123
18.6 In 1,1,2 trichloroethane, CHa2 Cl−CHb Cl2 , there are two types a and b of
inequivalent protons. Since the Hb is in the immediate neighbourhood of two elec-
tronegative chlorine atoms, its chemical shift is larger than that of the two Ha , whose
C atom is substituted with only one Cl. Due to the dipole-dipole interaction with Hb ,
the lines of the two Ha protons split into two lines with a spacing of JHa Hb and equal
intensity; the Hb resonance, in contrast, splits into three lines due to the coupling
with the two Ha , with a line spacing of JHa Hb and relative intensities in the ratio
1:2:1. The integrated intensity ratio of the resonance signals of Ha (two protons) to
Hb (one proton) is 2:1.
In the measured spectrum, one observes a doublet at δ = 3.95 ppm (Ha ) and
a triplet at δ = 5.77 ppm (Hb ). The line splitting is in each case JHa Hb = 6.0 Hz.
Furthermore, one observes a smaller solvent peak at δ = 7.28 ppm, which is caused
by CHCl3 impurities in the CDCl3 solvent.
18.7 In the spectrum of H3 a C−CH2 b −CH2 c −NO2 , the assignment of the signals
to the inequivalent proton species can be carried out noting the inductive effect of the
electron-attracting NO2 group: because of the lowest electron density and nuclear
shielding at the positions of the Hc protons, their resonance occurs at the lowest B
field, so that their chemical shift has the largest value:
δc = 4.38 ppm .
Taking into account the long-distance effects on the two other groups of protons,
one finds
Through the dipole-dipole interaction with the two Hb , the Hc line splits into a
triplet. Since there is no measurable additional splitting due to interactions with the
Ha , one concludes that the coupling constant Jac is negligible:
Jac ≈ 0 .
124 Solutions
The same result can be derived from the threefold splitting of the Ha signal.
It is valid only within the precision of the measurement, i. e. the resolution of the
spectrometer.
For the Hb line, due to the interactions with three protons of type Ha and two
protons of type Hc , one would expect a 4·3 = 12-fold splitting. From the multiplicity
of 6, however, it can be concluded that there is an interaction with five (for this
interaction) equivalent protons (5 + 1 = 6-fold splitting) and thus an equally strong
coupling of Hb to Ha and Hc :
Jba = Jbc .
In fact, small deviations from a simple sextet pattern are observed, since Jba = Jbc
is not precisely fulfilled.
18.8 a) In the molecule CH3 a CHb O, there are two types a and b of inequiva-
lent protons. Taking the inductive effect of the electronegative oxygen atom in the
aldehyde group into account, one sees that for the chemical shifts of the two protons,
δb > δa .
The precise numerical values can be taken from part b):
δa = 2.20 ppm and δb = 9.80 ppm .
The ratio of the integrated intensities of the signals of three nuclei of type Ha to that
from one nucleus of type Hb is approximately 3:1.
The Ha line splits into a doublet of equally intense lines with a spacing of
J = 2.9 Hz; the Hb resonance, in contrast, splits into a quartet with the same line
spacing and the relative intensity ratios 1:3:3:1.
b) The chemical shift δ is computed from the resonance-field strengths BT for
the frequency standard TMS and BS for the sample, according to the formula
BT − BS
δ = 106 · . (1)
BT
The linear relationship between δ and BS allows us to extract the difference ∆BS
of the magnetic resonance field strengths directly from the difference ∆δ between
the chemical shifts of two types of protons. Since for the standard, the chemical shift
is defined to be δT = 0, it corresponds to an external B0 field at a value of BT , so
that it follows from (1) that:
∆BS = (−) 10−6 BT ∆δ . (2)
With ∆δ = 7.6 ppm, one obtains
for B0 = 1.5 T : ∆BS = 1.14 · 10−5 T ,
for B0 = 7.0 T : ∆BS = 5.32 · 10−5 T .
The differences ∆BP of the resonance field strengths correspond to the differ-
ences between the local magnetic fields in the different regions of the molecule.
Chapter 18 125
From the coupling of the proton spin to the two deuterium spins, we thus find a
multiplet consisting of five equidistant lines (pentet; the line spacing is JHD ) with the
relative line intensities 1:2:3:2:1, as one can see from the number of possible combi-
nations for the total (combined) spin of the two D nuclei (m Iges = −2, −1, 0, 1, 2).
18.10 Due to diffusion, rotation, or other processes, the magnetic environment of
a spin is constantly changing, e. g. due to changes in its distance and angle to a
neighbouring dipole. In the model, this is simulated by superposing a statistically
fluctuating field onto the constant external magnetic field B0 , which takes on the
values +Bi and −Bi . The shift of the precession frequency of the spin relative to the
frequency ω0 in the B0 field alone is then given by
If τ is the average time during which the magnetic environment remains constant,
then it follows for the average phase shift δφ which the precessing spin undergoes
between two successive field jumps, relative to a spin in the field B0 , that
δφ = ± τ γBi (2)
Here, φ2 is the mean squared phase shift relative to a spin in the constant B0 field.
The spin contributes to the resonance signal approximately so long a its phase shift
is less than a value of 1 rad. The number n of steps required to reach this limit is
found from (4) to be
1
n= . (5)
τ2 γ 2 Bi2
126 Solutions
[!t]
Fig. S.29. The phase ϕ of a spin in a fluctuating magnetic field (· · · magnetic field B0 ± Bi ,
—– Phase shift ϕ relative to spins in only the B0 field)
The time required for n fluctuations of an average length τ, i. e. the time for a
sufficient phase loss of a spin relative to the spin in only the B0 field, is denoted as
the transverse relaxation time T2 in Bloch’s theory of magnetic resonance:
1
T2 = n τ = . (6)
τ γ 2 Bi2
∆ω = (∆ω0 )2 · τ . (9)
∆ω # ∆ω0 . (10)
Motional narrowing thus becomes more and more effective the shorter the mean
fluctuation time τ.
Chapter 18 127
18.11 In liquids, the fluctuations of the local magnetic field at the location of a spin
are often much more rapid than in a solid, in which neither diffusion nor rotation of
the molecules are effective. According to Eq. (6) from problem 18.10, the transverse
relaxation time T2 depends on the mean fluctuation time τ and the strength Bi of the
field fluctuations:
1
T2 = n τ = .
τ γ 2 Bi2
It is therefore longer in liquids (T2 ≈ 10−4 − 10 s) than in solids (T2 ≈ 10−4 s).
The shorter lifetime of the phase-coherent spin states in solids leads –due to the
uncertainty relation– to broader NMR lines (T2 : phase-loss time).
18.12 a) At a lower exchange frequency, one finds two distinct resonance signals,
which are separated by ∆ν = 39 Hz. The two lines begin to merge when their widths
∆ω L , determined by the lifetimes, correspond to their separation on the frequency
axis. A single line is accordingly observed when
The linewidth ∆ωL is coupled to the lifetime τ of the states (i. e. of the magnetic
environments):
1
∆ωL = . (2)
τ
From (1) and (2), we obtain
1
τ< , (3)
2π ∆ν
and thus for the exchange frequency νA = 1
τ between the different environments:
1
νA = = 2π ∆ν . (4)
τ
With the given value for ∆ν, one obtains
νA = 245 Hz .
Fig. S.30. Pulse sequence and echoes in the Carr-Purcell method. After M. Mehring: Princi-
ples of High Resolution NMR in Solids; Chap. 3 (Springer, Berlin, Heidelberg 1983)
Chapter 18 129
with t = n · 2τ.
18.15 We write the Schrödinger equation
iψ̇ = Hψ (1)
in the form
i
ψ̇ = − Hψ . (2)
Its formal solution is
i
ψ = e− ~ Ht ψ(0) . (3)
and likewise
n ∗
H ψ φdx = ψ ∗ H n φdx . (7)
Using the bra and ket notation, we can write with (4) and (9)
where
i i
DH = e ~ Ht D e− ~ Ht . (11)
whereby
1 0
|↑ = , |↓ = . (16)
0 1
If we set a = ceiφ/2 and b = ce−iφ/2 in this expression, we find for the expectation
value of the x component:
1 2 −iφ
|c| e + eiφ = |c| 2 cos φ , (24)
2
and correspondingly for the y component:
as well as
The expectation value of the spin vector thus undergoes a coherent rotational
motion.
18.17 We begin with the usual commutation relations,
and thus
obtaining
· 1
Iky Ilz = JIkx . (33)
2
132 Solutions
Vs = −µ B . (47)
In the usual experimental arrangement (see also problem 18.20), the spin is subjected
to a constant field B along the z direction and an oscillating field perpendicular to it
(48). Correspondingly, we choose kλ = (0, 0, k z ) and eλ = (0, e y , 0).
We then obtain
e 1 ωλ
Vs = ikλ eikλ z sx bλ + h.c. (50)
m 0 ωλ 2ε0 V
From this result, we can immediately read off the coupling constant that we are
seeking. We arrive at the “rotating-wave” approximation by investigating the motion
of the operators in the Heisenberg representation (without interactions between I and
B (48)). Then bλ ∼ e−iωλ t , I± ∼ eiΩt is found. In the neighbourhood of resonance,
Ω ≈ ωλ , the terms I+ bλ , I− b+ +
λ vary slowly, while the terms I+ b ∼ e
iΩt+iωλ t
and
I− b oscillate rapidly and make practically no contribution to the interaction energy.
They can therefore be neglected in (51).
18.20 We start with
i
ḃ+ = [H, b+ ] . (1)
Due to the commutation relations
it follows that
Chapter 19
19.1 The dipole-dipole interaction between an electron spin and the nuclear spins
leads to a hyperfine splitting of the ESR lines. The number of lines is given by the
number 2I + 1 of different possible orientations of the nuclear spin I relative to the
direction of the electronic spin. The spins of the participating nuclei are I = 0 for
12
C; I = 12 for 13 C, 1 H and 19 F; I = 1 for 2 D; and I = 32 for 35 Cl and 37 Cl.
b) In agreement with the notation of the H locations in the problem text (structural
formula), in 1-iodo naphthalene, the iodine substituent is located at an α position.
The interaction of the electronic spin with the remaining three α proton spins and
the four β spins then leads to a splitting into 20 lines which can be grouped into four
pentets. The intensity ratio of the group maxima is 1:3:3:1, and their spacing is aα .
In 2-iodo naphthalene, on the other hand, the iodine atom replaces a β proton,
so that a splitting into five quartets and thus likewise a total of 20 lines is observed.
The intensity ratios of the group maxima are 1:4:6:4:1, and their spacing is again aα .
The interaction with the spin of the 127I nucleus (nuclear spin 52 ) was neglected in
the above considerations. It would further split each of the lines into six sublines.
c) The substitution of one hydrogen by a methyl group leads in analogy to (b) to
a splitting of the ESR signal in each case into 20 lines. In addition, the interactions
with the three methyl protons produces a further quartet splitting of each line with
the intensity ratio (1:3:3:1) – the hyperfine structure thus includes all together 80
lines.
19.3 a) In the [NH2 ]• radical, the dipole-dipole interaction of the electronic spin
with the spin of the nitrogen nucleus 14 N (I = 1) leads to a splitting of the signal
into three lines of equal intensity, with a spacing of aN = 1.03 mT. The coupling
with the two proton spins I = 12 splits each of the three lines into a triplet (line
spacing aH = 0.35 mT, intensity ratio 1:2:1).
b) The ESR spectrum of the azide radical [14 N 3 ]• exhibits a hyperfine structure
with seven lines, which is caused by the spin-spin interaction of the free electron with
the total spin of the three nitrogen nuclei. The lines of the septet have the relative
intensities 1:3:6:7:6:3:1; cf. Figs. S.31 and S.32.
b) The assignment of the given values for the spin density, i , to the inequivalent
C positions in anthracene (see above) can be carried out by means of a comparison
with naphthalene. The spin density , and with it the coupling strength a, decrease
on going from the centre of the molecule outwards, and we find
the interaction of the electronic spin with the proton spins, starting from the spin
densities:
aα = Q α = (−) 0.434 mT ,
aβ = Q β = (−) 0.218 mT ,
aγ = Q γ = (−) 0.108 mT .
The interaction of the electronic spin with the three types of protons leads to the
following splittings (number of lines, relative intensity ratios, and line spacings):
Hα : 3 lines, 1:2:1, aα ,
Hβ : 5 lines, 1:4:6:4:1, aβ ,
Hγ : 5 lines, 1:4:6:4:1, aγ .
One thus expects a hyperfine-structure splitting of the ESR signal of anthracene
into 75 lines.
19.5 The resonance frequency ν of an electron in a magnetic field of strength B is
given by the relation
g µB
ν= B (1)
h
(µB = 9.274 · 10−24 Am2 : Bohr magneton). From it, with the given values for the
frequency and the B field, we can compute the g-factor of the electron:
hν
g= . (2)
µB B
Since the hyperfine-structure splitting of the signal is symmetric around the
centre of gravity of the lines, we take as the B field the average value of the two line
positions (B = 303.32 mT). From this, we obtain
g = 2.0022
for an electron in atomic hydrogen. The strength of the dipole-dipole interaction is
independent of the applied B field, so that we find the coupling constant directly
from the spacing of the two hyperfine-structure lines:
a = ∆B = 50.70 mT .
19.6 In the CH3 radical, the hyperfine structure of the ESR lines is due to the
interactions of the free electron spin with the three equivalent protons of nuclear spin
I = 12 . One observes a quartet, for which the relative line intensities of 1:3:3:1 can be
derived using Pascal’s triangle. In the triply-deuterated CD3 radical, an interaction
with three equivalent D nuclear spins of I = 1 occurs. The line intensities in the
resulting septet are determined by the family-tree method described in problem 19.3
b) to be 1:3:6:7:6:3:1.
138 Solutions
19.7 The six protons in the benzene molecule are chemically and magnetically
equivalent. This has two consequences: on the one hand, spin diffusion takes place
between the nuclei, i. e. there is a rapid exchange of their spin orientations. Any
differences in the interactions of the electron with the individual nuclear spins is
averaged out, so that one must treat the equivalent protons all together, i. e. as a total
spin. This picture also enters into the description of the dipole-dipole interaction for
the elucidation of the fine structure of NMR spectra.
On the other hand, the free electron of the benzene radical anions is localised to
the extent of 16 on each of the equivalent C atoms, so that its spin couples equally
strongly to each of the six protons. It is therefore irrelevant how the spin orientations
which contribute to a given total spin are distributed among the individual protons.
The rotation of the molecule as a whole has no influence at all upon these two
intramolecular effects. It therefore causes no wiping out of the hyperfine structure
owing to exchange phenomena.
In order to calculate the hypothetical exchange narrowing of the ESR signal,
we first briefly ignore the counterarguments given. The hyperfine-structure coupling
constant for the interaction of the free electron spin with the proton spins in benzene
is a = 0.375 mT. The hyperfine structure of the ESR signals vanishes when the
lifetime broadening νL of the individual lines becomes as large as the spacing ∆νHfs
of two neighbouring lines. The lifetime τ of a spin state is obtained from Heisenberg’s
uncertainty relation according to:
∆E · τ ≡ h ∆ν · τ = , (1)
and from it, the lifetime broadening of a hyperfine-structure line:
1
νL = ∆ν = = . (2)
hτ 2π τ
In the case of a benzene molecule rotating about its sixfold symmetry axis, the
lifetime of a particular spin state is limited by the rotational frequency νR . The
rotation leads to a rapid exchange of the nuclear spin positions at an exchange
frequency of
1
νA = = 6 νR . (3)
τ
It follows from this that
6νR
νL = , (4)
2π
and with
g µB
νL = ∆νHfs = a, (5)
h
one finally obtains the rotational frequency at which, according to this model, the
hyperfine structure should be averaged out:
π g µB
νR = a. (6)
3h
Chapter 19 139
r = 1.63 Å .
19.10
3 1 2 2 2
r12 − 3z 212 3
3 ∗
D= g µ Ψ ΨdV1 dV2 (1)
4 2 e B 5
r12
2 2
3 1 2 2 3 ∗ y12 − x12
E= g µ Ψ 3
ΨdV1 dV2 . (2)
4 2 e B 5
r12
Since, owing to the planarity of the molecules, the z component of the distance r12
of the triplet electrons can be neglected, the fine-structure parameter D is directly
correlated with r12 and thereby with the molecular size:
1
D∝ 3
. (2)
r12
Here, r12 can already be understood as the averaged distance. The larger the
molecule, the larger r12 , and the smaller the fine-structure constant D. We thus find
that
The experimental values are 0.15, 0.10, 0.07, and 0.06 cm−1 .
Chapter 19 141
|E| benzene < |E| naphthalene < |E| anthracene < |E| tetracene . (4)
The experimental values for these energies are 0, −0.013, −0.015, and −0.030 cm−1 .
b) Corresponding to the results in (a), one attributes a D value of 0.15 cm−1 to
benzene, while tetracene has the other extreme value of 0.06 cm−1 . With the aid
of Eq. (4) from problem 19.9, one can calculate from this the averaged electron
distances in the two molecules to be
∆I < 0 . (1)
The ADMR spectrum yields the transmitted intensity I at a fixed optical fre-
quency as a function of the wavelength of the applied microwave radiation. One
thus observes three signals, when the microwave frequency corresponds to one of
the transition frequencies between the triplet sublevels 0, D − E and D + E:
I: transmitted intensity;
I0 : irradiation intensity;
ε: extinction coefficient;
d: optical path length;
c: sample concentration;
S0 : fraction of the molecules in the S0 state.
Irradiation with microwaves leads to a change in the ground-state population by
∆S0 ; the transmitted light intensity thus becomes
∆I I − I
= = 10−ε ∆S0 c d − 1 = e−ε ln 10 ∆S0 c d − 1 . (5)
I I
This expression can be expanded up to the first-order term in the case of low
optical densities
OD = εc d , (6)
The fraction of molecules in the S0 ground state, relative to the overall number
of molecules, thus increases by 0.076%. This shows that ADMR is an extremely
sensitive method of measurement, which however also requires a correspondingly
sensitive detection apparatus.
Chapter 20 143
Chapter 20
20.2 The distance dependence of the energy transfer rate kET is given by
1
kET ∝ , (1)
r6
so that for the (critical) Förster radius and an arbitrary distance r1 , we can write the
relation
1
k1 6
k0 r06 = k1 r16 ⇐⇒ r0 = r1 . (2)
k0
In the case of twelve chain links, we find for the chain length and thus the distance
r1 between the donor and the acceptor:
r1 = 46.1 Å ,
r0 = 37.7 Å .
Chapter 22
22.1 One can, at least theoretically, make use of the entire inhomogeneous line-
width Γ for photochemical hole-burning. The width of the hole corresponds to twice
the homogeneous linewidth, which is due only to the lifetime limit:
2
γhole = 2 γh = . (1)
2π τ
With Γ = 700 cm−1 and γhole = 0.55 cm−1 , we calculate the maximum num-
ber n max of the holes to be burned to be
Γ
n max = = 1273 . (2)
γhole
The information density D of the optical data-storage medium can thus be
increased by a factor of the order of 103 :
bits bits
D = 108 2
· n max ≈ 1011 . (3)
cm cm2
We mention a few of the many practical problems which crop up in trying to
construct this type of optical storage medium:
– Cooling of the material to a low temperature, (4 K).
– Tuning of the laser to the individual address bits, both spatially and in its fre-
quency.
– The velocity of the photochemical reactions limits the writing speed.
– A satisfactory signal/noise ratio for reading requires a minimum readout time.
– Laser systems for the required wavelength range (diffraction limit λ2 !) are very
impractical. A fourth dimension could be included by making use of an holo-
graphic storage scheme.