Hdout Chap 5 5210 PDF

CHAPTER 5
MOLECULAR VIBRATIONS AND

TIME-INDEPENDENT PERTURBATION THEORY
OUTLINE
Homework Questions Attached
PART A: The Harmonic Oscillator and Vibrations of Molecules.
SECT TOPIC
1. The Classical Harmonic Oscillator
2. Math Preliminary: Taylor Series Solutions of Differential Equations
3. The Quantum Mechanical Harmonic Oscillator
4. Harmonic Oscillator Wavefunctions and Energies
5. Properties of the Quantum Mechanical Harmonic Oscillator
6. The Vibrations of Diatomic Molecules
7. Vibrational Spectroscopy
8. Vibrational Anharmonicity
9. The Two Dimensional Harmonic Oscillator
10. Vibrations of Polyatomic Molecules

PART B: The Symmetry of Vibrations + Perturbation Theory + Statistical
Thermodynamics
SECT TOPIC
1. Symmetry and Vibrational Selection Rules
2. Spectroscopic Selection Rules
3. The Symmetry of Vibrational Normal Modes:

Application to the Stretching Vibrations in Ethylene
4. Time Independent Perturbation Theory
5. QM Calculations of Vibrational Frequencies and Molecular Dissociation Energies
6. Statistical Thermodynamics: Vibrational Contributions to the Thermodynamic

Properties of Gases
7. The Vibrational Partition Function
8. Internal Energy: ZPE and Thermal Contributions
9. Applications to O2(g) and H2O(g)

Chapter 5 Homework
d2y
1. Consider the differential equation:  4 y
dx 2

Assume that the solution is of the form: y   a n x n  a 0  a1 x  a 2 x 2  a 3 x 3  ...
n 0
Develop “recursion relations” relating (1) a2 to a0 , (2) a3 to a1 , (3) a4 to a2
2. One of the wavefunctions of the Harmonic Oscillator is:

2  k
  A1 xe  x /2
 
 
(a) Calculate the normalization constant, A1 (in terms of )
(b) Determine <x> (in terms of )
(c) Determine <x2> (in terms of )
(d) Determine <p> (in terms of )
(e) Determine <p2> (in terms of )
(f) Determine <T>, average kinetic energy (in terms of )
(g) Determine <V>, average potential energy (in terms of )
3. Consider a two dimensional Harmonic Oscillator for which ky =9·kx. Determine the
energies (in terms of x) and degeneracies of the first 7 energy levels for this oscillator.
4. Consider the diatomic molecule, carbon monoxide, 12C16O, which has a fundamental
vibrational frequency of 2170 cm-1.
(a) Determine the CO vibrational force constant, in N/m.
(b) Determine the vibrational Zero-Point Energy, Eo, and energy level spaces,
E, both in kJ/mol.
5. The 35Cl2 force constant is 320 N/m. Calculate the fundamental vibrational frequency of
35
Cl2, in cm-1.
6. The 4 vibrational frequencies of CO2 are: 2349 cm-1, 1334 cm-1, 667 cm-1, 667 cm-1.
(a) Calculate the Zero-Point vibrational energy, i.e. E(0,0,0,0) in
(1) cm-1 (i.e. E/hc), (2) J, (3) kJ/mol.
(b) Calculate the energy required to raise the vibrational state to (0, 2,1,0) in
(1) cm-1 (i.e. E/hc), (2) J, (3) kJ/mol.
7. The fundamental vibrational frequency of 127I2 (observed by Raman spectroscopy) is 215
cm-1.
(a) Calculate the I2 force constant, k, in N/m.
(b) Calculate the ratio of intensities of the first “hot” band (n=1  n=2) to the
fundamental band (n=0  n=1) at 300 oC.
8. The Thermodynamic Dissociation Energy of H35Cl is D0 = 428 kJ/mol, and the

fundamental vibrational frequency is 2990 cm-1. Calculate the Spectroscopic
Dissociation Energy of H35Cl, De.
9. A particle in a box of length a has the following potential energy:
V(x)   x<0
V(x) = B 0  x  a/2
V(x) = 2B a/2  x  a
V(x)   x>a
Use first-order perturbation theory to determine the ground state energy of the particle in
this box. Use 1 = Asin(x/a) where A=(2/a)1/2 and E1 = h2/8ma2 as the unperturbed
ground state wavefunction and energy.
10. Use first-order perturbation theory to determine the ground state energy of the quartic
oscillator, for which:
2 d 2
H   x 4
2  dx 2
Use the Harmonic Oscillator Hamiltonian as the unperturbed Hamiltonian:

2 d 2 1 2
HO Hamiltonian: H   kx
2  dx 2 2
1/ 4
 x 2 / 2   k 1
Use  0  Ae where A    ,  2  2 and E0   and
   2
as the unperturbed ground state wavefunction and energy
Your answer should be in terms of k, , ħ, , and 
11. The Fundamental and First Overtone vibrational frequencies of HCl are 2885 cm-1 and
~) and the anharmonicity constant (x ).
5664 cm-1. Calculate the harmonic frequency ( e
12. The symmetric C-Br stretching vibration of CBr4 has a frequency of 270 cm-1. Calculate
the contribution of this vibration to the enthalpy, heat capacity (constant pressure),
entropy and Gibbs energy of two (2) moles of CBr4 at 800 oC.
13. Three of the fundamental vibrational modes (CH bending) in methylenecyclopropene
(C2V) are:
1(a2) = 860 cm-1 2(b1) = 1270 cm-1 3(b2) = 740 cm-1
(a) Determine whether each fundamental mode is active or inactive in the IR

and Raman Spectra.
(b) Determine whether each combination mode below is active or inactive

in the IR and Raman Spectra.
(i) 1 + 3
(ii) 2 - 3
H H
C2V E C2 V(xz) V’(yz) C
C
A1 1 1 1 1 z x2, y2, z2 C C
A2 1 1 -1 -1 Rz xy H z H
B1 1 -1 1 -1 x, Ry xz
x
B2 1 -1 -1 1 y, Rx yz
DATA
h = 6.63x10-34 J·s 1 J = 1 kg·m2/s2

ħ = h/2 = 1.05x10-34 J·s 1 Å = 10-10 m
c = 3.00x108 m/s = 3.00x1010 cm/s k·NA = R
NA = 6.02x1023 mol-1 1 amu = 1.66x10-27 kg
k = 1.38x10-23 J/K 1 atm. = 1.013x105 Pa
R = 8.31 J/mol-K 1 eV = 1.60x10-19 J
R = 8.31 Pa-m3/mol-K
me = 9.11x10-31 kg (electron mass)
 1   1
 
2
xe   x dx 
2
e   x dx 
0 2  0 2
 1   1
 
2 2
x 2 e   x dx  x 3e   x dx 
0 4  0 2 2
 3  1 1
  sin sin  2 x 
2
x 4 e   x dx  2
( x)dx  x
0 8 2
 2 4
Some “Concept Question” Topics
Refer to the PowerPoint presentation for explanations on these topics.
 Asymptotic solution to HO Schrödinger equation
 The Recursion Relation for the HO solution and quantization of energy levels
 Vibrational Zero Point Energy
 Vibrational Anharmonicity
 Interpretation of the vibrational force constant, k [curvature of V(x)]
 IR and Raman activity
 “Hot” bands
 Effect of vibrational anharmonicity on energy levels and vibrational frequencies
 Scaling of computed vibrational frequencies
 Equipartition of vibrational energy and heat capacity

Chapter 5
Molecular Vibrations and

Time-Independent Perturbation Theory
Part A: The Harmonic Oscillator and

Vibrations of Molecules
Part B: The Symmetry of Vibrations

+ Perturbation Theory
+ Statistical Thermodynamics
Slide 1
Part A: The Harmonic Oscillator and Vibrations of Molecules
• The Classical Harmonic Oscillator

• Math Preliminary: Taylor Series Solution of Differential Eqns.
• The Quantum Mechanical Harmonic Oscillator
• Harmonic Oscillator Wavefunctions and Energies
• Properties of the Quantum Mechanical Harmonic Oscillator
• The Vibrations of Diatomic Molecules
• Vibrational Spectroscopy
• Vibrational Anharmonicity
• The Two Dimensional Harmonic Oscillator
• Vibrations of Polyatomic Molecules
Slide 2
1
The Classical Harmonic Oscillator
The Potential Energy of a Diatomic Molecule
A B
R
V(R)
0
Re
Harmonic Oscillator Approximation
V(R)  ½k(R-Re)2 k is the force constant
or V(x)  ½kx2 x = R-Re

Slide 3
Hooke’s Law and Newton’s Equation
m1 m2
x = R - Re
Force:
Newton’s Equation: where
Reduced Mass
Therefore:
Slide 4
2
Solution
Assume:
or
or
Slide 5
Initial Conditions (like BC’s)
Let’s assume that the HO

starts out at rest stretched
out to x = x0.
x(0) = x0
and
Slide 6
3
Conservation of Energy
Potential Energy (V) Kinetic Energy (T) Total Energy (E)
t = 0, , 2, ... x = x0
t = /2, 3/2, ... x=0
Slide 7
Classical HO Properties
Energy: E = T + V = ½kx02 = Any Value i.e. no energy quantization
If x0 = 0, E = 0 i.e. no Zero Point Energy
Probability: E = ½kx02
P(x)
-x0 0 +x0
x
Classical Turning Points Slide 8
4

Slide 9
Math Preliminary: Taylor Series

Solution of Differential Equations
Taylor (McLaurin) Series
Any “well-behaved” function can

be expanded in a Taylor Series
Example:
Slide 10
5
Example:
0 1 0 3
Slide 11
Taylor (McLaurin) Series
Any “well-behaved” function can

be expanded in a Taylor Series
Example:
A Differential Equation
Solution:
Slide 12
6
Taylor Series Solution
Our goal is to develop a “recursion formula” relating

a1 to a0, a2 to a1... (or, in general, an+1 to an)
Specific
Recursion
Formulas:
Coefficients of xn must be equal for all n
a1 = a0
2a2 = a1 a2 = a1/2 = a0/2
3a3 = a2 a3 = a2/3 = a0/6
Slide 13
a1 = a0
a2 = a0/2
a3 = a0/6
Power Series
Expansion for ex
General Recursion Formula
Coefficients of the two series may be equated

only if the summation limits are the same.
Therefore, set m = n+1  n=m-1
and m=1 corresponds to n = 0
or
Slide 14
7

Slide 15
The Quantum Mechanical Harmonic Oscillator

Schrödinger Equation
Particle vibrating against wall
m
x = R - Re
Two particles vibrating against each other
m1 m2
x = R - Re
Boundary Condition: 0 as x  

Slide 16
8
Solution of the HO Schrödinger Equation
Rearrangement of the Equation
Define
Slide 17
Should we try a Taylor series solution?
No!! It would be difficult to satisfy the Boundary Conditions.
Instead, it’s better to use:
That is, we’ll assume that  is the product of a Taylor Series, H(x),
and an asymptotic solution, asympt, valid for large |x|
Slide 18
9
The Asymptotic Solution
We can show that the

asymptotic solution is For large |x|
Plug in
Note that asympt satisfied the BC’s;

i.e. asympt  0 as x 
Slide 19
A Recursion Relation for the General Solution
Assume the general solution is of the form
If one: (a) computes d2/dx2

(b) Plugs d2/dx2 and  into the Schrödinger Equation
(c) Equates the coefficients of xn
Then the following recursion formula is obtained:
Slide 20
10
Because an+2 (rather than an+1) is related to an, it is best to consider
the Taylor Series in the solution to be the sum of an even and odd series
Even Series Odd Series
From the recursion formula: Even Coefficients
Odd Coefficients
a0 and a1 are two arbitrary constants
So far: (a) The Boundary Conditions have not been satisfied

(b) There is no quantization of energy
Slide 21
Satisfying the Boundary Conditions: Quantization of Energy
So far, there are no restrictions on  and, therefore, none on E
Let’s look at the solution so far:
Does this solution satisfy the BC’s: i.e.   0 as x  ?
It can be shown that: unless n
Therefore, the required BC’s will be satisfied if, and only if, both
the even and odd Taylor series terminate at a finite power.
Slide 22
11
We cannot let either Taylor series reach x.
We can achieve this for the even or odd series by setting

a0=0 (even series) or a1=0 (odd series).
We can’t set both a0=0 and a1=0, in which case (x) = 0 for all x.
So, how can we force the second series to terminate at a finite

value of n ?
By requiring that an+2 = 0•an for some value of n.
Slide 23
If an+2 = 0•an for some value of n, then the required BC will

be satisfied.
Therefore, it is necessary for some value of the integer, n, that:
This criterion puts restrictions on the allowed values of  and,

therefore, the allowed values of the energy, E.
Slide 24
12
Allowed Values of the Energy
Earlier Definitions Restriction on 
n = 0, 1, 2, 3,...
Quantized Energy Levels
n = 0, 1, 2, 3,...
or
Slide 25

Slide 26
13
HO Energies and Wavefunctions
Harmonic Oscillator Energies
Angular Frequency:
Circular Frequency:
Energy
Wavenumbers:
where
Slide 27
Quantized Energies
Only certain energy levels are allowed
and the separation between levels is:
Energy
The classical HO permits any value of E.
Zero Point Energy

The minimum allowed value for the
energy is:
The classical HO can have E=0.
Note: All “bound” particles have a minimum ZPE.

This is a consequence of the Uncertainty Principle.
Slide 28
14
The Correspondence Principle
The results of Quantum Mechanics must not contradict those of
classical mechanics when applied to macroscopic systems.
The fundamental vibrational frequency of the H2 ħ = 1.05x10-34 J•s
molecule is 4200 cm-1. Calculate the energy level c = 3.00x108 m/s
spacing and the ZPE, in J and in kJ/mol. = 3.00x1010 cm/s
NA = 6.02x1023 mol-1
Spacing:
ZPE:
Slide 29
Macroscopic oscillators have much lower frequencies than

molecular sized systems. Calculate the energy level spacing and
the ZPE, in J and in kJ/mol, for a macroscopic oscillator with a
frequency of 10,000 cycles/second. ħ = 1.05x10-34 J•s
c = 3.00x108 m/s
= 3.00x1010 cm/s
NA = 6.02x1023 mol-1
Spacing:
ZPE:
Slide 30
15
Harmonic Oscillator Wavefunctions
Application of the recursion formula yields a

different polynomial for each value of n.
These polynomials are called Hermite
polynomials, Hn
or
where
Some specific solutions
n=0 Even
n=1 Odd
n=2 Even
n=3 Odd
Slide 31
 2
Slide 32
16
Quantum Mechanical vs. Classical Probability
Classical
P(x) minimum at x=0
E = ½x0 2
P(x) = 0 past x0
P(x) QM (n=0)
P(x) maximum at x=0
P(x)  0 past x0
-x0 0 +x0
x
Classical Turning Points
Slide 33
Correspondence
Principle
E = ½x02
n=9
P(x)
Note that as n increases, P(x)
approaches the classical limit.
For macroscopic oscillators
-x0 0 +x0
x n > 106
Classical Turning Points

Slide 34
17

Slide 35
Properties of the QM Harmonic Oscillator

Some Useful Integrals
Remember
If f(-x) = f(x)
Even Integrand
If f(-x) = -f(x)
Odd Integrand
Slide 36
18
Wavefunction Orthogonality
- < x < 
- < x < 
- < x < 
<0|1>
Odd Integrand
Slide 37
Wavefunction Orthogonality
- < x < 
- < x < 
- < x < 
<0|2>
Slide 38
19
We performed many of the calculations below on 0 of the
HO in Chap. 2. Therefore, the calculations below will be
on 1.
- < x < 
Normalization
from
HW Solns.
Slide 39
Positional Averages
<x>
from
HW Solns.
<x2>
from
HW Solns.
Slide 40
20
Momentum Averages
<p>
from
HW Solns.
<p2>
^
from
HW Solns.
Slide 41
Energy Averages
Kinetic Energy Potential Energy
from from
HW Solns. HW Solns.
Total Energy
Slide 42
21

Slide 43
The Vibrations of Diatomic Molecules

The Potential Energy
A B
V(R)
0 R
Re
Define: x = R - Req
Expand V(x) in a Taylor series about x = 0 (R = Req)
Slide 44
22
V(R)
0
Re
By convention
By definition
of Re as minimum
Slide 45
V(R)
0
Re
The Harmonic Oscillator Approximation

Ignore x3 and higher order terms in V(x)
where
Slide 46
23
The Force Constant (k)
The Interpretation of k
V(R)
0
Re
i.e. k is the “curvature” of the plot, and represents the “rapidity”

with which the slope turns from negative to positive.
Another way of saying this is the k represents the “steepness”
of the potential function at x=0 (R=Re).
Slide 47
Correlation Between k and Bond Strength

V(R)
V(R)
0 0
Re Re
Do Do
Small k Large k
Small Do Large Do
Do is the Dissociation Energy of the molecule, and

represents the chemical bond strength.
There is often a correlation between k and Do.
Slide 48
24
Note the approximately linear correlation between
Force Constant (k) and Bond Strength (Do).
Slide 49

Slide 50
25
Vibrational Spectroscopy
Energy Levels and Transitions
Selection Rule
(+1 for absorption,
n = 1
-1 for emission)
IR Spectra: For a vibration to be IR active, the dipole moment

must change during the course of the vibration.
Raman Spectra: For a vibration to be Raman active, the polarizability

must change during the course of the vibration.
Slide 51
Transition Frequency
n  n+1
Wavenumbers:
Note:
The Boltzmann Distribution
The strongest transition corresponds to: n=0  n=1
Slide 52
26
Calculation of the Force Constant
Units of k
Calculation of k
Slide 53
The IR spectrum of 79Br19F contains a single line at 380 cm-1

Calculate the Br-F force constant, in N/m. h=6.63x10-34 J•s
c=3.00x108 m/s
c=3.00x1010 cm/s
k=1.38x10-23 J/K
1 amu = 1.66x10-27 kg
1 N = 1 kg•m/s2
Slide 54
27
Calculate the intensity ratio, ,for the 79Br19F vibration at 25 oC.
h=6.63x10-34 J•s
c=3.00x108 m/s
c=3.00x1010 cm/s
k=1.38x10-23 J/K
~ = 380 cm-1
Slide 55
The n=1  n=2 transition is called a hot band, because its

intensity increases at higher temperature
Dependence of hot band intensity on frequency and temperature
~
Molecule  T R
79Br19F 380 cm-1 25 oC 0.16
79Br19F 380 500 0.49
79Br19F 380 1000 0.65
H35Cl 2880 25 9x10-7
H35Cl 2880 500 0.005
H35Cl 2880 1000 0.04
Slide 56
28

Slide 57
Vibrational Anharmonicity
V(R)
0
Re
Harmonic Oscillator
Approximation:
The effect of including vibrational anharmonicity in treating the vibrations

of diatomic molecules is to lower the energy levels and decrease the
transition frequencies between successive levels.
Slide 58
29
V(R)
0
Re
A treatment of the vibrations of diatomic molecules which includes

vibrational anharmonicity [includes higher order terms in V(x)]
leads to an improved expression for the energy:
~
 is the harmonic frequency and xe is the anharmonicity constant.
Measurement of the fundamental frequency (01) and first
overtone (02) [or the "hot band" (1 2)] permits determination
of ~ and xe. See HW Problem Slide 59
Energy Levels and Transition Frequencies in H2
3 15,400
3 13,930
E/hc [cm-1]
2 11,000
2 10,250
1 6,600
1 6,330
0 2,200 0 2,170
Harmonic Actual
Oscillator
Slide 60
30
Anharmonic Oscillator Wavefunctions
 n = 10 2
 n = 2 2
 n = 0 2
Slide 61

Slide 62
31
The Two Dimensional Harmonic Oscillator
The Schrödinger Equation
The Solution: Separation of Variables
The Hamiltonian is of the form:
Therefore, assume that  is of the form:
Slide 63
=
E
Exx Ey
The above equation is of the form, f(x) + g(y) = constant.

Therefore, one can set each function equal to a constant.
E = Ex + Ey
Slide 64
32
The above equations are just one dimensional HO Schrödinger equations.
Therefore, one has:
Slide 65
Energies and Degeneracy
Depending upon the relative values of kx and ky, one may have
degenerate energy levels. For example, let’s assume that ky = 4•kx .
11/2 g=3
40 02 21
9/2 g=2
30 11
E [ ħ ]
7/2 g=2
20 01
5/2 g=1
10
3/2 g=1
00
Slide 66
33

Slide 67
Vibrations of Polyatomic Molecules
I’ll just outline the results.
If one has N atoms, then there are 3N coordinates. For the i’th. atom,
the coordinates are xi, yi, zi. Sometimes this is shortened to: xi.
 = x,y or z.
The Hamiltonian for the N atoms (with 3N coordinates), assuming

that the potential energy, V, varies quadratically with the change in
coordinate is:
Slide 68
34
After some rather messy algebra, one can transform the Cartesian
coordinates to a set of “mass weighted” Normal Coordinates.
There are 3N-6 Normal Coordinates.
Each normal coordinate corresponds to the set of vectors showing

the relative displacements of the various atoms during a given vibration.
For example, for the 3 vibrations of water, the Normal Coordinates
correspond to the 3 sets of vectors you’ve seen in other courses.
O O O
H H H H H H
Slide 69
In the normal coordinate system, the Hamiltonian can be written as:
Note that the Hamiltonian is of the form:
Therefore, one can assume:
and simplify the Schrödinger equation by separation of variables.

Slide 70
35
One gets 3N-6 equations of the form:
The solutions to these 3N-6 equations are the familiar Harmonic

Oscillator Wavefunctions and Energies.
As noted above, the total wavefunction is given by:
The total vibrational energy is:
Or, equivalently:
Slide 71
In spectroscopy, we commonly refer to the “energy in wavenumbers”,

which is actually E/hc:
The water molecule has three normal modes, with fundamental

frequencies: ~1 = 3833 cm-1, ~
2 = 1649 cm-1, ~3 = 3943 cm-1.
What is the energy, in cm-1, of the (112) state (i.e. n1=1, n2=1, n3=2)?
Slide 72
36
The water molecule has three normal modes, with fundamental
frequencies: ~1 = 3833 cm-1, ~
2 = 1649 cm-1, ~3 = 3943 cm-1.
What is the energy difference, in cm-1, between (112) and (100),

i.e. E(112)/hc – E(100)/hc ?
This corresponds to the frequency of the combination band in which

the molecule’s vibrations are excited from n2=0n2=1 and
n3=0n3=2.
Slide 73
37
Chapter 5
Molecular Vibrations and

Time-Independent Perturbation Theory
Part B: The Symmetry of Vibrations

+ Perturbation Theory
Slide 1
Part B: The Symmetry of Vibrations + Perturbation Theory

• Symmetry and Vibrational Selection Rules
• Spectroscopic Selection Rules
• The Symmetry of Vibrational Normal Modes:
• Time Independent Perturbation Theory
• QM Calculations of Vibrational Frequencies and Dissoc. Energies
• Statistical Thermodynamics: Vibrational Contributions to
the Thermodynamic Properties of Gases
• The Vibrational Partition Function Function
• Internal Energy: ZPE and Thermal Contributions
• Applications to O2(g) and H2O(g)
Slide 2
1
Symmetry and Vibrational Selection Rules
x
-
By symmetry: f(-x) = -f(x)
Slide 3
Consider the 1s and 2px orbitals in a hydrogen atom.
+ - +
- + + x
By symmetry: Values of the integrand for -x are the negative of

values for +x; i.e. the portions of the integral to the
left of the yz plane and right of the yz plane cancel.
If you understand this, then you know all (or almost all) there is to
know about Group Theory.
Slide 4
2
The Direct Product
There is a theorem from Group Theory (which we won’t prove)

that an integral is zero unless the integrand either:
(a) belongs to the totally symmetric (A, A1, A1g) representation
(b) contains the totally symmetric (A, A1, A1g) representation
unless
The question is: How do we know the representation of an integrand

when it is the product of 2 or more functions?
Slide 5
The product of two functions belongs to the representation

corresponding to the Direct Product of their representations
How do we determine the Direct Product of two representations?
Simple!! We just multiply their characters (traces) together.
Slide 6
3
C2V E C2 V(xz) V’(yz)
A1 1 1 1 1
A2 1 1 -1 -1
B1 1 -1 1 -1
B2 1 -1 -1 1
B1xB2 1 1 -1 -1 A2
A2xB1 1 -1 -1 1 B2
A2xB2 1 -1 1 -1 B1
A2xA2 1 1 1 1 A1
B1xB1 1 1 1 1 A1
When will the Direct Product be A1?
Only when the two representations are the same.

(This is another theorem that we won’t prove)
Slide 7
What if the integrand is the product of three functions?

e.g.
The representation of the integrand is the Direct Product of the

representations of the three functions.
i.e.
What is f if one of the 3 functions belongs to the totally

symmetric representation (e.g. if (c) = A1) ?
Therefore unless
Slide 8
4
When will the Direct Product be A1?
Only when the two representations are the same.

(This is another theorem that we won’t prove)
A minor addition.
When considering a point group with degenerate (E or T)

representations, then it can be shown that the product of two
functions will contain A1 only if the two representations are the same.
e.g. E x E = A1 + other
Slide 9
Based upon what we’ve just seen:

unless
Therefore, the integral of the product of two functions vanishes

unless the two functions belong to the same representation.
Slide 10
5
What if the integrand is the product of three functions?
e.g.
The representation of the integrand is the Direct Product of the

representations of the three functions.
i.e.
What is f if one of the 3 functions belongs to the totally

symmetric representation (e.g. if (c) = A1) ?
Therefore unless
Slide 11

Slide 12
6
Spectroscopic Selection Rules
When light (of frequency ) is shined on a sample, the light’s

electric vector interacts with the molecule’s dipole moment, which
adds a perturbation to the molecular Hamiltonian.
The perturbation “mixes” the ground state wavefunction (0 = init ) with
various excited states (i = fin). A simpler way to say this is that the
light causes transitions between the ground state and the excited
states.
Consider a transition between the ground state (0 = init ) and the
i’th. excited state (i = fin).
Time dependent perturbation theory can be used to show that

the intensity of the absorption is proportional to the square
of the “transition moment”, M0i.
Slide 13
The transition moment is:
^ is the dipole moment operator:


Thus, the transition moment has x, y and z components.

Slide 14
7
The above equation leads to the Selection Rules in various areas
of spectroscopy.
The intensity of a transition is nonzero only if at least one component
of the transition moment is nonzero.
That’s where Group Theory comes in.

As we saw in the previous section, some integrals are zero due to
symmetry.
Stated again, an integral is zero unless the integrand belongs to

(or contains) the totally symmetry representation, A, A1, A1g...
Slide 15
Selection Rules for Vibrational Spectra

Infrared Absorption Spectra
The equation governing the intensity of a vibrational infrared absorption

is allowed (i.e. the vibration is IR active) is:
init and fin represent vibrational wavefunctions of the initial

state (often the ground vibrational state, n=0) and final state (often
corresponding to n=1).
Slide 16
8
A vibration will be Infrared active if any of the three components
of the transition moment are non-zero; i.e. if
or
or
Slide 17
Raman Scattering Spectra
When light passes through a sample, the electric vector creates

an induced dipole moment, ind, whose magnitude depends
upon the polarizability, . The intensity of Raman scattering depends
on the size of the induced dipole moment.
Strictly speaking,  is a tensor (Yecch!!)
I have used the fact that the  tensor is symmetric; i.e. ij = ji
There are 6 independent

components of : xx , yy , zz , xy , xz , yz
Slide 18
9
Therefore, a vibration will be active if any of the following
six integrals are not zero.
u = x, y, z and v = x, y, z
uv has the same symmetry properties as the product uv;

i.e. xx belongs to the same representation as xx,
yz belongs to the same representation as yz, etc.
Therefore, a vibration will be Raman active if the direct product:
for any of the six uv combinations; xx, yy, zz, xy, xz, yz
Slide 19

Slide 20
10
The Symmetry of Vibrational Normal Modes
C2h E C2 i h
We will concentrate on the four C-H
Ag 1 1 1 1 x2,y2,z2,xy
stretching vibrations in ethylene, C2H4.
Bg 1 -1 1 -1 xz,yz
Ethylene has D2h symmetry. However, Au 1 1 -1 -1 z
because all 4 C-H stretches are in the Bu 1 -1 -1 1 x,y
plane of the molecule, it is OK to use
the subgroup, C2h. 1 1 1 1 1 ag
y 2 1 1 1 1 ag
3 1 -1 -1 1 bu
x
4 1 -1 -1 1 bu
1 2 3 4
(3030 cm-1) (3100 cm-1) (3110 cm-1) (2990 cm-1)
ag ag bu bu
Slide 21
Symmetry of Vibrational Wavefunctions
One Dimensional Harmonic Oscillator
n=0
n=1
n=2
Harmonic Oscillator Normal Mode: k

Normal Coordinate: Qk
n=0
n=1
n=2
Slide 22
11
Total Vibrational Wavefunction of Polyatomic Molecules
Ground
State:
Singly
Excited State:
Slide 23
C-H Stretching Vibrations of Ethylene

C2h E C2 i h
IR Activity of Fundamental Modes Ag 1 1 1 1 x2,y2,z2,xy
Bg 1 -1 1 -1 xz,yz
Ag:
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
Ag vibrations are IR Inactive
Slide 24
12
IR Activity of Fundamental Modes C2h E C2 i h
Ag 1 1 1 1 x2,y2,z2,xy
Bu: Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
Bu vibrations are IR Active and polarized perpendicular to the axis.

Slide 25
Raman Activity of Fundamental Modes C2h E C2 i h

Ag 1 1 1 1 x2,y2,z2,xy
Ag: Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
Ag vibrations are Raman Active

Slide 26
13
Raman Activity of Fundamental Modes C2h E C2 i h
Ag 1 1 1 1 x2,y2,z2,xy
Bu: Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
Bu vibrations are Raman Inactive
Slide 27
The Shortcut C2h E C2 i h

Ag 1 1 1 1 x2,y2,z2,xy
Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
Corky: Hey, Cousin Mookie. Wotcha doing all that work for?
There’s a neat little shortcut.
Mookie: Would you please stop looking for shortcuts?
They can get you in trouble.
Corky: But look!! If there’s an x,y or z attached to the representation,
then the vibration’s IR active; Bu vibrations are IR Active.
Ag vibrations are IR Inactive.
If there’s an x2, y2, etc. attached to the representation,
then the vibration’s Raman active; Ag vibrations are Raman Active.
Buvibrations are Raman Inactive.
Mookie: How do you determine the activity of a combination mode?

Corky: What’s a combination mode?
Slide 28
14
IR Activity of Combination Modes C2h E C2 i h
Ag 1 1 1 1 x2,y2,z2,xy
2 + 4 Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
2 + 4 is IR Active and polarized perpendicular to the axis.

Slide 29
IR Activity of Combination Modes C2h E C2 i h

Ag 1 1 1 1 x2,y2,z2,xy
3 - 4 Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
3 - 4 is IR Inactive.
Slide 30
15
Raman Activity of Combination Modes C2h E C2 i h
Ag 1 1 1 1 x2,y2,z2,xy
2 + 4 Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
2 + 4 is Raman Inactive.
Slide 31
Raman Activity of Combination Modes

C2h E C2 i h
3 - 4 Ag 1 1 1 1 x2,y2,z2,xy
Bg 1 -1 1 -1 xz,yz
Au 1 1 -1 -1 z
Bu 1 -1 -1 1 x,y
3 - 4 is Raman Active.
Slide 32
16
Slide 33
Time Independent Perturbation Theory

Introduction
One often finds in QM that the Hamiltonian for a particular problem

can be written as:
H(0) is an exactly solvable Hamiltonian; i.e.
H(1) is a smaller term which keeps the Schrödinger Equation from

being solvable exactly.
One example is the Anharmonic Oscillator:
H(0) H(1)
Exactly Solvable Correction Term
Slide 34
17
where
In this case, one may use a method called “Perturbation Theory” to
perform one or more of a series of increasingly higher order corrections
to both the Energies and Wavefunctions.
Some textbooks** outline the method for higher order corrections.

However, we will restrict the treatment here to first order perturbation
corrections
We will use the notation: and
e.g. Quantum Chemistry (5th. Ed.), by I. N. Levine, Chap. 9
Slide 35
First Order Perturbation Theory
where
Assume: and
One can eliminate the two terms involving the product of two small corrections.
One can eliminate two additional terms because:
Slide 36
18
Multiply all terms by (0)* and integrate:
H(0) is Hermitian. Therefore:
Plug in to get:
Therefore:
is the first order perturbation theory

correction to the energy.
Slide 37
Applications of First Order Perturbation Theory

PIB with slanted floor
Consider a particle in a box with the potential:
 
V(x)
V0
For this problem:
0
0 a
x
The perturbing potential is:
Slide 38
19
Integral Info
We will calculate the first order correction to the nth energy level.
In this particular case, the correction to all energy levels is the same.
Independent of n
Slide 39
Anharmonic Oscillator
Consider an anharmonic oscillator with the potential energy of the form:
We’ll calculate the first order perturbation theory correction to the ground
state energy.
For this problem:
The perturbing potential is:
Slide 40
20
Note: There is no First order Perturbation Theory correction due
to the cubic term in the Hamiltonian.
However, there IS a correction due to the cubic term
when Second order Perturbation Theory is applied.
Slide 41
Brief Introduction to Second Order Perturbation Theory

As noted above, one also can obtain additional corrections to the energy
using higher orders of Perturbation Theory; i.e.
En(0) is the energy of the nth level for the unperturbed Hamiltonian
En(1) is the first order correction to the energy, which we have called E
En(2) is the second order correction to the energy, etc.
The second order correction to the energy of the nth level is given by:
where
Slide 42
21
If the correction is to the ground state (for which we’ll assume n=1), then:
Note that the second order Perturbation Theory correction is actually

an infinite sum of terms.
However, the successive terms contribute less and less to the overall
correction as the energy, Ek(0), increases.
Slide 43

• QM Calcs. of Vibrational Frequencies and Dissoc. Energies
Slide 44
22
The Potential Energy Curve of H2
E(cal) =2(-0.49982) hartrees

= -0.99964 hartrees (au)
Emin(cal) = -1.17253 hartrees (au)
Re(cal) = 0.742 Å
Re(exp) = 0.742 Å
Calculation at QCISD(T)/6-311++G(3df,3pd) level Slide 45
The Dissociation Energy
D0: Thermodynamic
Dissociation Energy De: Spectroscopic
Dissociation Energy
De(cal) = E(cal) – Emin(cal) = 0.17289 au •2625.5 kJ/mol / au
De(cal) = 453.9 kJ/mol
D0(exp) = 432 kJ/mol

Slide 46
23
Relating De to D0
D0: Thermodynamic
Dissociation Energy
De = D0 + Evib = D0 + (1/2)h
H 2: ~
(cal) = 4403 cm-1 [QCISD(T)/6-311++G(3df,3pd)]
~
versus (exp) = 4395 cm-1
The experimental frequency is the “harmonic” value,
corrected from the observed anharmonic frequency.
Slide 47
D0: Thermodynamic
Dissociation Energy
De = D0 + Evib = D0 + (1/2)h De(cal) = 453.9 kJ/mol
D0(cal) = De(cal) –Evib

= 453.9 – 26.4
= 427.5 kJ/mol
D0(exp) = 432 kJ/mol
Slide 48
24
Calculated Versus Experimental Vibrational Frequencies
H2O
(Harm)a (cal)b (cal)c

3943 cm-1 3956 cm-1 4188 cm-1
3833 3845 4070
1649 1640 1827
(a) Corrected Experimental Harmonic Frequencies
(b) QCISD(T)/6-311+G(3df,2p)
(c) HF/6-31G(d)
Lack of including electron correlation raises computed frequencies.
Slide 49
Harmonic versus Anharmonic Vibrational Frequencies

H2O
(exp)z (Harm)a (cal)b (cal)c
3756 cm-1 3943 cm-1 3956 cm-1 4188 cm-1
3657 3833 3845 4070
1595 1649 1640 1827
(z) Actual measured Experimental Frequencies
(a) Corrected Experimental Harmonic Frequencies
(b) QCISD(T)/6-311+G(3df,2p)
(c) HF/6-31G(d)
Lack of including electron correlation raises computed frequencies.
Slide 50
25
Differences between Calculated and Measured
Vibrational Frequencies
There are two sources of error in QM calculated vibrational
frequencies.
(1) QM calculations of vibrational frequencies assume that the

vibrations are “Harmonic”, whereas actual vibrations are
anharmonic.
Typically, this causes calculated frequencies to be approximately
5% higher than experiment.
(2) If one uses “Hartree-Fock (HF)” rather than “correlated electron”
calculations, this produces an additional ~5% increase in the
calculated frequencies.
To correct for these sources of error, multiplicative “scale factors”

have been developed for various levels of calculation.
Slide 51
An Example: CHBr3
(exp)a (cal)b (scaled)c
3050 cm-1 3222 cm-1 3061 cm-1
1149 (E) 1208 (E) 1148 (E)
669 (E) 691 (E) 656 (E)
543 546 519
223 228 217
155 (E) 158 (E) 150 (E)
(a) Measured “anharmonic” vibrational frequencies.

(b) Computed at QCISD/6-311G(d,p) level
(c) Computed frequencies scaled by 0.95
Slide 52
26
Another Example: CBr3•
(exp)a (cal)b (scaled)c

773 (E) cm-1 799 (E) cm-1 759 (E) cm-1
??? 324 308
??? 235 223
??? 164 (E) 156 (E)
(a) Measured “anharmonic” vibrational frequencies.

(b) Computed at QCISD/6-311G(d,p) level
(c) Computed frequencies scaled by 0.95
Slide 53
Some Applications of QM Vibrational Frequencies
(1) Aid to assigning experimental vibrational spectra

One can visualize the motions involved in the
calculated vibrations
(2) Vibrational spectra of transient species

It is usually difficult to impossible to experimentally measure
the vibrational spectra in short-lived intermediates.
(3) Structure determination.

If you have synthesized a new compound and measured
the vibrational spectra, you can simulate the spectra of
possible proposed structures to determine which pattern
best matches experiment.
Slide 54
27
Slide 55
Statistical Thermodynamics: Vibrational Contributions

to Thermodynamic Properties of Gases
Remember these?
Slide 56
28
Slide 57
The Vibrational Partition Function
HO Energy Levels:
The Partition Function
where
If v/T << 1 (i.e. if /kT << 1), we can convert the sum to an integral.
Let's try O2 ( 
~ = 1580 cm-1 ) at 298 K.
Sorry Charlie!! No luck!!

Slide 58
29
Simplification of qvib
Let's consider:
We learned earlier in the chapter that any

function can be expanded in a Taylor series:
It can be shown that the Taylor series for 1/(1-x) is:
Therefore:
Slide 59
and
For N molecules, the total vibrational partition function, Qvib, is:
Slide 60
30
Some comments on the Vibrational Partition Function
If we look back at the development leading to qvib and Qvib, we see that:
(a) the numerator arises from the vibrational Zero-Point Energy (1/2h)
(b) the denominator comes from the sum over exp(-nh/kT)
The latter is the "thermal" contribution to qvib because all terms above
n=0 are zero at low temperatures
In some books, the ZPE is not included in qvib; i.e. they use n = nh.
In that case, the numerator is 1 and they then must add in ZPE
contributions separately
ZPE Term Thermal Term
In further developments, we'll keep track of the two terms individually.
Slide 61

Slide 62
31
Internal Energy
UZPEvib Uthermvib
ZPE Contribution
This is just the vibrational Zero-Point

energy for n moles of molecules
or
Slide 63
Thermal Contribution
Slide 64
32
Although this expression is fine, it's commonly rearranged, as follows:
or
Slide 65
Limiting Cases
Low Temperature: Because the denominator

(T  0) approaches infinity
High Temperature:
(v << T)
The latter result demonstrates the principal of equipartition of vibrational

internal energy: each vibration contributes RT of internal energy.
However, unlike translations or rotations, we almost never reach the

high temperature vibrational limit.
At room temperature, the thermal contribution to the vibrational internal
energy is often close to 0.
Slide 66
33
Slide 67
Numerical Example
 = 1580 cm-1 ) at 298 K.

Let's try O2 ( ~
Independent of
Temperature
vs. RT = 2.48 kJ/mol
Thus, the thermal contribution to the vibrational internal energy

of O2 at room temperature is negligible.
Slide 68
34
A comparison between O2 and I2
I2: ~ = 214 cm-1  v = 309 K
T O2 I2 RT
(K) (kJ/mol) (kJ/mol) (kJ/mol)
298 0.009 1.41 2.48
500 0.20 3.00 4.16
1000 2.16 7.10 8.31
2000 8.92 15.4 16.6
3000 16.7 23.7 24.9
Because of its lower frequency (and,therefore, more closely spaced

energy levels), thermal contributions to the vibrational internal energy
of I2 are much more significant than for O2 at all temperatures.
At higher temperatures, thermal contributions to the vibrational internal
energy of O2 become very significant.
Slide 69
Enthalpy
Qvib independent of V
Therefore:
and:
Similarly:
Slide 70
35
Heat Capacity (CVvib and CPvib)
Independent of T
It can be shown that in the limit, V << T, CVvib  R
Slide 71
Numerical Example
 = 1580 cm-1 ) at 298 K (one mole).

Let's try O2 ( ~
vs. R = 8.314 J/mol-K
Slide 72
36
A comparison between O2 and I2
I2: ~ = 214 cm-1  v = 309 K
Vibrational Heat Capacities (CPvib = CVvib)

T O2 I2
(K) (J/mol-K) (J/mol-K)
298 0.23 7.61
500 1.85 8.05
1000 5.49 8.25
2000 7.47 8.30
3000 7.93 8.31
Vibrational contribution to heat capacity of I2 is greater because of

it's lower frequency (i.e. closer energy spacing)
The heat capacities approach R (8.31 J/mol-K) at high temperature.
Slide 73
Entropy
Slide 74
37
Numerical Example
 = 1580 cm-1 ) at 298 K (one mole).

Let's try O2 ( ~
"Total" Entropy
Chap. 3 Chap. 4
O2: Smol(exp) = 205.1 J/mol-K at 298.15 K
We're still about 5% lower than experiment, for now.
Slide 75
The vibrational contribution to the entropy of O2 is very low at 298 K.

It increases significantly at higher temperatures.
T Svib
298 K 0.035 J/mol-K
500 0.49
1000 3.07
2000 7.86
3000 10.82
Slide 76
38
Output from G-98 geom. opt. and frequency calculation on O2 (at 298 K)
QCISD/6-311G(d)
E (Thermal) CV S
KCAL/MOL CAL/MOL-K CAL/MOL-K
TOTAL 3.750 5.023 48.972
ELECTRONIC 0.000 0.000 2.183 G-98 tabulates the sum of
TRANSLATIONAL 0.889 2.981 36.321
ROTATIONAL 0.592 1.987 10.459
UZPEvib + Uthermvib even though
VIBRATIONAL 2.269 0.055 0.008 they call it E(Therm.)
Q LOG10(Q) LN(Q)
TOTAL BOT 0.330741D+08 7.519488 17.314260
TOTAL V=0 0.151654D+10 9.180853 21.139696
VIB (BOT) 0.218193D-01 -1.661159 -3.824960
VIB (V=0) 0.100048D+01 0.000207 0.000476
ELECTRONIC 0.300000D+01 0.477121 1.098612
TRANSLATIONAL 0.711178D+07 6.851978 15.777263
ROTATIONAL 0.710472D+02 1.851547 4.263345
We got 9.46 + 0.009 = 9.47 kJ/mol (sig. fig. difference)
(same as our result)
We got 0.035 J/mol-K (sig. fig. difference)

Slide 77
Helmholtz and Gibbs Energy
Qvib independent of V
O2 ( ~ = 1580 cm-1 ) at 298 K (one mole).
Slide 78
39
Polyatomic Molecules
It is straightforward to handle polyatomic molecules, which have

3N-6 (non-linear) or 3N-5 (linear) vibrations.
Energy:
Partition Function
Therefore:
Slide 79
Thermodynamic Properties
Therefore:
Thus, you simply calculate the property for each vibration separately,
and add the contributions together.
Slide 80
40
Comparison Between Theory and Experiment: H2O(g)
For molecules with a singlet electronic ground state and no low-lying

excited electronic levels, translations, rotations and vibrations are the
only contributions to the thermodynamic properties.
We'll consider water, which has 3 translations, 3 rotations and 3 vibrations.
Using Equipartition of Energy, one predicts:
Htran = (3/2)RT + RT CPtran = (3/2)R + R = (5/2)R
Hrot = (3/2)RT CProt = (3/2)R
Hvib = 3RT CPvib = 3R
Low T Limit: Htran + Hrot = 4RT CPtran + CProt = 4R
High T Limit: Htran + Hrot + Hvib = 7RT CPtran + CProt + CPvib= 7R
Slide 81
Calculated and Experimental Entropy of H2O(g)
Slide 82
41
Calculated and Experimental Enthalpy of H2O(g)
Slide 83
Calculated and Experimental Heat Capacity (CP) of H2O(g)
Slide 84
42
Translational + Rotational + Vibrational Contributions to O2 Entropy
Unlike in H2O, the remaining contribution (electronic) to the

entropy of O2 is significant. We'll discuss this in Chapter 10.
Slide 85
Translational + Rotational + Vibrational Contributions to O2 Enthalpy
There are also significant additional contributions

to the Enthalpy.
Slide 86
43
Translational + Rotational + Vibrational Contributions to O2 Heat Capacity
Notes: (A) The calculated heat capacity levels off above ~2000 K.
This represents the high temperature limit in which the
vibration contributes R to CP.
(B) There is a significant electronic contribution to
CP at high temperature. Slide 87
44

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CHAPTER 5

MOLECULAR VIBRATIONS AND

Homework Questions Attached

PART A: The Harmonic Oscillator and Vibrations of Molecules.

1. The Classical Harmonic Oscillator

2. Math Preliminary: Taylor Series Solutions of Differential Equations

3. The Quantum Mechanical Harmonic Oscillator

4. Harmonic Oscillator Wavefunctions and Energies

5. Properties of the Quantum Mechanical Harmonic Oscillator

6. The Vibrations of Diatomic Molecules

9. The Two Dimensional Harmonic Oscillator

10. Vibrations of Polyatomic Molecules

1. Symmetry and Vibrational Selection Rules

2. Spectroscopic Selection Rules

3. The Symmetry of Vibrational Normal Modes:

4. Time Independent Perturbation Theory

5. QM Calculations of Vibrational Frequencies and Molecular Dissociation Energies

6. Statistical Thermodynamics: Vibrational Contributions to the Thermodynamic

7. The Vibrational Partition Function

8. Internal Energy: ZPE and Thermal Contributions

9. Applications to O2(g) and H2O(g)

Develop “recursion relations” relating (1) a2 to a0 , (2) a3 to a1 , (3) a4 to a2

2. One of the wavefunctions of the Harmonic Oscillator is:

8. The Thermodynamic Dissociation Energy of H35Cl is D0 = 428 kJ/mol, and the

9. A particle in a box of length a has the following potential energy:

Use the Harmonic Oscillator Hamiltonian as the unperturbed Hamiltonian:

1(a2) = 860 cm-1 2(b1) = 1270 cm-1 3(b2) = 740 cm-1

(a) Determine whether each fundamental mode is active or inactive in the IR

(b) Determine whether each combination mode below is active or inactive

C2V E C2 V(xz) V’(yz) C

h = 6.63x10-34 J·s 1 J = 1 kg·m2/s2

Refer to the PowerPoint presentation for explanations on these topics.

 Asymptotic solution to HO Schrödinger equation

 Vibrational Zero Point Energy

 Interpretation of the vibrational force constant, k [curvature of V(x)]

 IR and Raman activity

 Effect of vibrational anharmonicity on energy levels and vibrational frequencies

 Scaling of computed vibrational frequencies

 Equipartition of vibrational energy and heat capacity

Molecular Vibrations and

Part A: The Harmonic Oscillator and

Part B: The Symmetry of Vibrations

Part A: The Harmonic Oscillator and Vibrations of Molecules

• The Classical Harmonic Oscillator

Harmonic Oscillator Approximation

V(R)  ½k(R-Re)2 k is the force constant

or V(x)  ½kx2 x = R-Re

Hooke’s Law and Newton’s Equation

Newton’s Equation: where

Initial Conditions (like BC’s)

Let’s assume that the HO

Potential Energy (V) Kinetic Energy (T) Total Energy (E)

t = 0, , 2, ... x = x0

t = /2, 3/2, ... x=0

If x0 = 0, E = 0 i.e. no Zero Point Energy

• The Classical Harmonic Oscillator

Math Preliminary: Taylor Series

Taylor (McLaurin) Series

Any “well-behaved” function can