QUANTUM CHEMISTRY

AUTHOR Dr. K.P.Patel

(M.Sc., M.Ed., Ph.D., Chemistry) (Principal)
Arts, Science and Commerce College Lunawada Dist. Panchmahal,Gujarat (India)
PUBLISHED BY The New Era International Publishing House HQ. At &
Po. Chaveli., Ta Chansma,
All rights reserved. Any person who does any unauthorized act in relation to this publication may
be liable to criminal prosecution and civil claims for damages.
First Publication: 15th May, 2015
Copyright: Author (c) Dr. K.P.Patel
ISBN:- 978 1 512 23771 9
Price: Rs.750/- INDIA $ 15 OUTSIDE INDIA
PUBLISHED BY The New Era International Publishing House HQ. At &
Po. Chaveli., Ta Chansma,

PREFACE
This book has been written for the students of under- graduate and post graduate level of the various universities in
India. A special feature of the book is that the text has been illustrated with a large number of line diagrams and
the data presented in the form of numerous tables for reference and comparison. In the preparation of text standard
works and review by renowned author have been freely consulted. At the end of the book will be found useful by
those who wish to make a more details study of the topics discussed.
However revealing of errors if any by the students and teachers which have missed attention and providing
suggestions for further improvement of the book would be deemed a great favour not only to Author but also to the
students community as a whole which would be gratefully acknowledged by the author.
I feel proud and happy in remembering at this juncture all those whose inspiration , encouragement and co-
operation have made my excellence book.
- Author Dr. K.P.Patel

INDEX
CHAPTER -1 STARTING OF WAVE MECHANICS ...................... 01-12
Introduction Black Body Redation Helsenberg Uncertainly Principle Interpretation of The
Schrodinger Equation Time Dependent Schrodinger Wave Equation Eigen Values and Eigen
Function Normalization and Orthogonality
CHAPTER -2 THE BASIC POSTULATES OF QUANTUM MECHANICS .... 13-31
First Portulates of Quantum Mechanics Second Portulates of Quantum Mechanics Operators
Some Conventions using Operators Liner Operators Itermition Operators Eigen Values
Important theroms of Hermitan Operator How to Construct Operators? Total Energy of of a
System Third Postulates
CHAPTER -3 QUANTUM MECHANICS OF SIMPLE SYSTEM WITH THE CON
POTENTIAL ENERGY ............................ 32-51
Particles in A Box problems Free Particle Zero Point Energy (ZPE) Particle in three
Dimensional Box Degerency Conservative System Orthogulity Eigen values Energy Levels
CHAPTER -4 SYSTEM WHERE THE POTENTIAL ENERGY IS NOT CONSTANT :
.............................................. 52-
Hydrogen Atom _ One Electron Problem Central Feild Problem Seperation of Variable Solution
of Solution of Equation Equation Solution of R Equation Wave Function of the H Like Atom
SCF Method
CHAPTER -5 APPROXIMATION METHOD .......................................79- 101 Variation Method
Time Indipendent – Perturbation Theory Perturbation theory for non-Degenerate System
Application of Parturbation Secular Equation VSIP Theory Ladder Operators
Chapter-1 Starting of wave mechanics
Introduction :
The dynamic behaviour of macroscopic objects with which we come in to contact in daily life is governed by
classical or Newtonian mechanics based on newton’s three well-known laws of motion. It was only around the turn
of the present century when phenomena like black body radiation, photoelectric effect, Compton effect and line
spectrum of hydrogen atom were discovered that the inadequacy of classical mechanics was realized after a
successful period of over three hundred years. Beginning with the revolutionary proposal of quantization of Max
Planck in 1900 a new science governing the dynamical behaviour of subatomic constituents especially of electrons
has evolved over a period of only about thirty years. This new science, known as quantum Mechanics, has been
serving admirably in rationalizing chemical behaviout. Like any other theory or model, the quantum mechanics is
also based on certain basic postulates. The only difference is that these postulates relate to atomic and molecular
properties that are far from everyday experience and so are likely to appear strange and even unreasonable never
the less these are to be taken on faith, the only justification being their ability to predict and correlate experimental
facts. Again, quantum mechanics is an abstract mathematical model and calls for a great deal of tolerance and a
good background of non-too-difficult mathematics to fully appreciate it. The practical results emerging from dry
looking formalism are simply amazing.
There are two variants of quantum mechanics according to mathematical tools used. One is called “Matrix
Mechanics” (Werner Heisenberg, 1925) based on use of matrix algebra while the other is called “Wave mechanics”
(Ervin Schrodinger, 1926) which is based on classical wave theory and de Broglie’s wave practicle duality. The
latter being relatively simpler is more easily appreciated of the two. It is based on differential equations. However,
what is referred to as quantum mechanics today is fusion of some aspects of both formalisms. It must be
emphasized that in spite of the confirmed validity of the formalisms of quantum mechanics in measurements
involving atomic structure, spectra, covalent bonds, free radicals, mechanisms mechnics still remains a model
which we do not fully understand. However, the bewildering sequence of events beginning with Planck’s quantum
hypothesis in 1900 and culminating in quantum mechanical formalisms of Heisenberg and Schrodinger in 1926
represent a total recognization of the fundamental philosophy of science. In particular, they have forced an
essential change in out attitude toward experimental observation. The rigid determinism of classical mechanics
must give way to acceptance of the impossibility of experimentally determining or predicting the exact properties
of an individual particle ar a given moment in time. Rather, we must deal with the statistical regularities which
characterize a large number of measurements on a single particle. We must deal with probabilities rather than
certainties. Quantum mechanics thus introduces a margin of uncertainity in our ability to measure and to know
nature.
BLACK BODY RADIATION- PLANK’S QUANTUM HYPOTHESIS: The prefect black body is one which
obsorbs the heat radiation of
whatever wavelength incident on it. It neither reflects nor transmits any of
the incident radition and therefore appear black. But in nature no such body
exists. But some body made up carbon obsorbs the most of the incident
raditions. Radiation coming from the black body at a particular temperature
shown in the fig.
The Characteristic of the curve.
(i) energy is not uniformaly distributed in the radiation spectrum of the black body
(ii) intensity is maxium at a particular wave length, which is characteristic of the temperatures of the radiation
body.
According to classical theory the average energy associated with each degrees of freedom is KT. Rayleigh-Jeans
law deduced with help of classical theory says the energy per unit volume in the frequency range
and
+ d
is given by According to this expression the energy emitted by a
black body increases with the frequency and becomes infinite at large frequency. The experimentally obsorved
radiation curve is complete disagreement with this conclusion. Since experimental curve shows that energy
radiated at a particular temperature becomes zero both at lowar and higher frequency of shown in figure (1.1).
To clear this problem in 1900, Planck introduce a hypothesis known as Planck’s hypothesis and according to this,
“the black body radiation chamber is filled up not only with radiation but also the simple harmonic oscillator of
molecular dimension known as Planck’s oscillator which can vibrate the all possible frequency”.
Plank assume that the energy of an oscillator of frequency various discreatly as that is multiples of small unit
called quanta. This quanta of radiation is called photons. The energy of the photon is proportional to the frequency
of the radiation that where h= 6.626 x 10-34 Jsec. The total energy of the oscillator which would be partly kinetic
and partly potential must be = nh, where n= 0,1,2,3........ So the radiation would not be a continuous one, the
discreat energies as O, h, 2h, ...... Now the Planck radiation law deduced with the help of Planck quantum theory
gives the energy desity interms of wave length belonging the range and as.toward experimental observation. The
rigid determinism of classical mechanics must give way to acceptance of the impossibility of experimentally
determining or predicting the exact properties of an individual particle ar a given moment in time. Rather, we must
deal with the statistical regularities which characterize a large number of measurements on a single particle. We
must deal with probabilities rather than certainties. Quantum mechanics thus introduces a margin of uncertainity in
our ability to measure and to know nature.
HEISENBERG UNCERTAINTY PRINCIPLE :
This law of nature, first stated by Werner Heisenberg in 1927 emphasizes the fundamental difference between
quantum mechanics and classical mechanics. One of the basic tenets of classical mechanics is that it is possible to
know all dynamical variable of a system to any desired degree of accuracy. Such a strict determinism is untenable
while dealing with quantum-mechanical systems (the microworld of atoms, molecules). In quantum mechanics we
have to accept that there is a natural limit on the relative accuracy with which certain pairs of variables can be
known. This was expressed as :
“precise measurements of the position and momentum of a particle like an electron
cannot be accoplished simultaneously.”
Expressed mathematically : x . px h
(h is the Planck constant)
If the position and momentum of a particle could be determined very precisely under quantum conditions then the
particle-wave would have both a well-defined wavelength and a well-defined position. This seems contradictory.
Imagine an experiment which simultaneoulsy determines the position and momentum of an electron. Say two
precise measurements of position at different times are made from the elapsed time electron follows at once.
However, in order to locate the electron with such precision it is necessary to “see” the electron by shining a
radiation of extremely short wavelength i.e. photons of very large momentum on it. The interaction of the photon
with the electron px)min would obviously change the momentum of the electron. Thus the very act of measuring
its precise position renders its momentum imprecise. h represents the natural limit in the simultaneous precision
px)min of position and
momentum, i.e. x . h )
Note that :
(1) the uncertainty principle is of no consequence in the macroworld due to very small magnitude of h.
(2) Since x is related to wave description and px to particle description, the uncertainty principle emphasizes the
mutual exclusiveness of these two aspects which are to be regarded complementary.
(3) Not all measurements are subject to this fundamental restriction. The uncertainty principle applies to
canonically conjugate pairs of variables, like energy (E) and time (t)
or angular momentum ( P ) and angle ( ). Thus
E.th
.ph
(4) The uncertainty principle as stated here is a specific case of the generalized form which can be derived from
quantum theory for any pair of variables, A and B. The generalized form of Heisenberg uncertainty principle is
A,BA.B2i
IfA is $ andB isx , $ x P
x , Px i H (prove yourself) $ i Hx , Px
iHx.Px2i

x.

PHx2
INTERPRETATION OF :
If must be noted that in using 2 to represent “electron (particle) density” in quantum mechanics. We have drawn
analogy with classical electrodynamic theory where
the energy density is represented in terms of field vectors H and E as 1
R
E 8 z 2 dxdydz
Where Z is a new field vector defined as
ZEiH
Moreoever shows a typical behaviour of a vector. Just as a vector can be resolved in to components.
AiAxjAykAz
Similarly, any arbitrary state of a system can be expressed as a linear combination
of eigen states, i
a 1 1 a 2 2 ............... a n n n Following Dirac may be treated as a vectore (called the state vector) and represented as
‘Ket ’,
.
The associated dual vectore (equivalent of the complex conjugate *) is called the ‘bra ’ and is represented as
. In this Dirac notation, the combination of bra and ket
|
*d
|H|
*Hd
In quantum mechanics, the length of a ket vector has no physical meaning (i.e., multuplication by a scalar does not
alter the state; if is a solution, then a is also a solution); only the direction matters.
THE SCHRODINGER EQUATION (H
=E

Stable wave function has node & Antinode. Hight of wave is increased from node to antinode. While it is
decreased from Antinode to node. So changing of energy
with the changing of particle. We call it wave function
is depend on time. But for the system of atom
is free from atom so.
A sin wt
A sin
.t s
HIF\ VFJT"SF/ V[S RS| 5}6" SZJF ,FUTM ;DI w =
)
A sin 2
.

A sin 2
.
……….(A) ( VFJT"SF/
TZ\U,\AF.
t=?,
= x WFZM4 = )

Differentiation of Eq (A) =
A cos
and

. A sin =
 .
………… (B)
Total energy of particle is given by T + V
E=T+V
wher, T = ½ mv2
T=

P2 = 2Tm ( P = mv J[UDFG ) ………(C)

By the eq. or De Broqlie
=
P2

…………….(D)
relationship between (C) + (D)
2Tm =

……………(E)
put the value of (E) in Eq. (B)

xTx
Now, E = T + V
T=E–V

(E- V) .

(E- V)
= 0 ……………. (F)

(F) is the Schrödinger eq. for a single particle in one dimensions for a single particle in three dimensions is. +

(E- V) =0
(
 +

(E- V) =0
+

(E- V) = 0 where
=Laplasian operation multiply by

+V]
=E
……………… (G)
H
=E
…….. ( H ) where, H = Hemiltonian operator. Eq. ( H ) is the short form of
Schrodinger equation.
TIME DEPENDENT SCHRODINGER WAVE EQUATION
SJMg8D lDS[lG;SGF ;DIGF 5NGM ;DFJ[X VlT DCtJGM K[P SM. 56 1F6[ EF{lTS 5|6F,L DF8[ TZ\U lJW[I
,[JFDF\ VFJ[ TM T[ lA\N]V[ 5|6F,LGF OST U]6WDM"G]\ H J6"G SZT] GYLP 5Z\T] 5|lT1F6[
T[ 5|6F,LG]\ JT"G
56 H6FJ[ K[P VF CSLSTG[ UFl6TLI ZLT[

J0[ ZH} SZJFDF\ VFJ[ K[P H[ t ;DI DF8[ K[P

SJMg8D I\+XF:+GL RMYL VlEWFZ6F 5|DF6[ (4th According to postulate of quantum mechanism ) TZ\U
lJW[IGL ;DI ;FY[ J'lâ GLR[GF zMl0\HZ ;DLP J0[ ZH} SZJFDF\ VFJ[ K[P
=
(r,t)
(r) .exp (-

E(t) ) ……………… (1)

where{
.exp (-

E(t) ) (t)
Eq….(1) G]\ lJS,G SZTF\ (detrantial of Eq …..(1) is)

………………..(2) {
= Hemeltonian operator) =
E
=
Now,
=

+ V(r) …………(3)(a)
pnt the valu of
in Eq ……….(2)
[
 + V(r)]
=

…………(3)
CJ[

,BTF\
t

…………..(4)
TZ\U lJW[I VG[
p5Z VFWFlZT A[ TZ\U lJW[IM J0[ ZH} SZL XSFI K[P VF TZ\UlJW[IM VG]S|D[
r
VG[
K[P T[YL
G[ A[ :JT\+ Vl:TtJ WZFJTF\\ TZ\U lJW[IGF ;FNF U]6FSFZYL NXF"JL XSFI P
(r,t) =
(r)
(t )…………….(5)
rG[ VG],1FLG[ ;DLP (5) G]\ lJ38G SZTF\

=
(t)

……………(6)
rG[ VG],1FLG[ ;DLP (6) G]\ OZLYL lJS,G SZTF\

=
(t)

……………(7)

T[JL H ZLT[ ;DLP (5) G] t G[ VG],1FLG[ lJS,G SZTF\4 =

……………(8) (r)

;DLP (5), (7) & (8) GL lS\DTM ;DL (4) DF\ D]STF4 .

+ Vr .

(t) =

;DLP (9) G[
J0[ EFUTF\4

+ Vr =

………….(10)
;DLP (10) DF\ 0FPAFPG]\ 5N DF+ r 5Z VFWFlZT K[P HD6L AFH]G] 5N t p5Z VFWFlZT K[P 5lZ6FD[ AgG[
5NG]\ V,ULSZ6 YFI K[P ;DLPGL AgG[ AFH]VMG[[ VR/F\S "E" ;FY[ ;ZBFJTF\ A[ V,U ;DLP D/[ K[ H[ GLR[
D]HA K[P
(1)

+ Vr
=E
………….(11)
(2)

=E
……………………..(12)
Eq ---(11) V[ ;DIYL :JT\+ ;DLP K[P HIFZ[ ;DLP (12) ;DI VFWFlZT K[P
EIGEN VALUES AND EIGEN FUNCTIONS
If we implies operator
on any any wave function , Resulting this wave function back with multifunction of any constant
values, we say this function is Eigen function and equation is Eigen equation which write as under.
=a

--------- ( 1)
(Where, = Eigen Function a= Eigen Value
and Eq – (1) is Eigen Equation.)
Schrodinger equation H
=E
is also eigen equation. Where operator,
eigen function n & E eigen value. If the value of
gives the acceptable solution of
schrodinger equation which known as a eigen function and resulting the total value of E by the satisfy solution of
schrodinger equation which known as a eigen value for the system in quantum mechanics.
NORMALIZATION AND ORTHOQONALITY
Information of any system of moving particle
gets by the wave function value of
2 dv, gives the probability to finding the

in small value dv of any place of system. Now if

(particle) is in any system the probability to finding the in system is sure. (
D/JFGL ;\EFJGF RMSS; CMI K[P)
H-Atom has on
. So,
is in the area of H- Atom therefore probability to finding the
in this area will be one. Value of probability of
in small value dv in various place of this area is known by
2 .dv. So, integral of
2 .dv. fof al area gives the value of probability to finding the
in the area of this system.
The integral of this wave function over the entire space in the box must be equal to unity because there is only one
electron and at all times it is some where in the box . Therefore

dx = 1
If any wave function follow this condition known as normalized wave function. If
is not normalized at all times multiply by N'
 )2 dv = 1 where, N = Normalized constant
N2
2
dv = 1
2
dv =
Consider the normalized wave function
n and
corresponding to two different states of an electron in a box, it is found that for n n'

dx = 0
The wave functions for different states of this system are thus orthogonal. This property of orthogonality between
any two different states ensures that the various states are truly independent of one another.
Chapter-2 The Basic Postulates of Quantum Mechanics :
First Postulates of Quantum Mechanics
(a) The state of a dynamical system is described as fully as possible by a function which is a function of all the
coordinates qi of the particles of the system and of time. i.e. = (qi, t). This function is called the state function or
the wave function.The concept of is the single most fundamental and extremely important concept in quantum
mechanics. It contains every possible information on the state described by it. The use of the phrase “as fully as
possible” emphasises the natural limit to the knowability of a quantum mechanical system as embodied in the
Heisenberg’s uncertainty principle.
It is to be noted that is generally complex. i.e., contains i = 1 and therefore, unlike thermodynamic state functions
or more precisely their differences, cannot be measured by direct experiment. (This need not disturb us since
properties depend on
which is always real. is the complex conjugate of and is obtained by changing the sign of i where it occurs in ). is a
function of all the coordinates of all the particles present in the system and of time.
( q i , t ) q i =generalized coordinates (s) of ith particles. Thus for a single particle, one dimensional (x) system, =
(x, t) and for a singleparticles three-dimensional system = (x,y,z,t). For the general system of n
particles, = (x, y, z, ...... xn , yn , zn , t). Consider (x, t). The value of space coordinate x defines the location of the
particle (or equivalently a particular configuration of the system) at time t. The permissible range of valies of x, sat
x , defines all
possible configurations of or the configuration space available to the system. In the general case, specifying, at a
given instant t, all the space coordinates of all the n particles. viz. x1 y1 z1 x2 y2 z2 ........ xn yn zn (a total of 3n
coordinates) defines the cofiguartion (distribution of constituent particles) at the particular time t and specifying
the total range of values of each coordinates, say
x i = 1, 2, ........... n y
z
defines the configuration space available to the system.
It has been said earlier that we have to be content with probabilistic descriptions while dealing with quantum
mechanical systems and this forms the substance of the remainder of Postulate-1.
(b) The nature of the function is such that * d is the probability that
the system has a configuration described by at time t. The state function must be “well-behaved” i.e., finite, single-
valued, continuous and quadratically integrable (in other words, a Class Q function). note that, by postulate, is
connected with probability, though not directly but through . Since whereas is generally complex (probability must
be real) is always real.
According to P.1(b), if = (x, t) then dx represents the probability of finding the particle at x (i.e. its coordinate
between x and x + dx) at time t. Similarly, for a many - particle system with
( q i , t ) ( x 1 y 1 z 1 x 2 y 2 z 2 .......................... x N y N z N , t ) ----- (4)
* dx 1 dy 1 dz 1 .....................dz N * d represents the probability that, at time t, particle 1 is found in a small volume
element dV 1 at ( x 1 y 1 z 1 ) (i.e. with its x-coordinate between x 1 and x 1 dx 1 , y-coordinate between y 1 and y 1
dy 1 and z-coordinate between z 1 and z 1 dz 1 , small volume element dV 2 at ( x 2 y 2 z 2 ) , particle-3 in a small
volume
element dV 3 at ( x 3 y 3 z 3 ) etc.
It is to be noted that the quantum mechanical probability is to be interpreted in a
statistical sense. Thus, operationally, * d represents the relative number of times in a large number of
measurements that the system is found in a particular configuration descrived by at time t. This is the Born
interpretation of and * is called the probability density or distribution function. The latter part of P.1(b) concerning
restriction on well-behaved automatically follow since must be in accord with physical reality. Since the
probability cannot be allowed to be infinite (infinite probability would mean certainty and the uncertainty principle
will be violated) and has to have just one value at a given point, the requirements that be finite and singlevalued
are obvious. Continuity requirement follows similarly. By square integrable it is meant that integrated probability
must equal a finite number i.e.
........... * d
= Q (overall
configuration space)
obviously since all the particles must lie somewhere in the configuration space the integrated probability density
must be unity, i.e.,
*d1
all space
The function is then said to be normalized (to unity). We shall generally work
with normalized wave function. Note : * *2 and molecular problems. If
P is also interpreted as “electron density” in atomic ( x ) ( x ) 2 P ( x ) represents the number of electrons (or a
fraction of an electron in a single electron case) present between x and x + dx.
SECOND POSTULATES OF QUANTUM MECHANICS
If A is and operator associated with an observable A and there is a set of identical systems known to be in the state
n that is an eigenfunction of A , i.e., A a ( a n is a number)
nnn

then, if an experimentalist makes a series of measurements of the property A, it will get the same result a n . It is
only under this condition that an experiment will give a precise result.” OR
“The only possible values that can be observed for a dynamical variable in an assembly of systems are the
eigenvalues a i in the equation.
A i a ii
Where A is the operator for the variable and i is any well-behaved eigenfunction of A .
(vi) Expectation value of an operator : (mean velue theorem)
if is not an eigenfunction of A ,
Aa'
The operation by the operator (equivalent to an attempt to experimentally measure the property A) changes the
state and so repeated measurements will not give the same result. Thus the property A in such a case is note well-
defined (or sharp; it cannot be determined with complete certainty. In a series of measurements on identical
systems, we shall get a range of values. where a precise value is impossible to obtain, we shall have to be content
with only the mean or the average value (the expectation value of the operator) obtained as stated in P.2(b).
(b) MEAN VALUE THEOREM
When a great many measurements of any dynamical variable A are made on an assembly of identical systems all
described by a function that is not an eigenfunction
of the operator A associated with the vatiable A, a distribution of results will be obtained. Although we cannot
predict the result of any particular measurement, the average or mean value of A,

A will be given by

A * A d / * d (general)

A
* A d ( normalized) Is is easy to show that the expectation value is same as the eigenvalue if is an eigenfunction of
A.
Let a and * d 1 ( normalized)A

A*Ad*ada*da

OPERATORS :
In order to extract the information contains in it is necessary to “operate” on it. We require operators. The concept
of an operator is introduced in P.2.
“For every dynamical variable there must be assigned a linear, Hermitian operator. The physical properties of the
variable can be deduced from the mathematial properties of the associated operator.”
We have been using operators all along (e.g. d/dx,

, ( )2 , etc.) The only thing is that we have not thought about them apart from the functions on which they
operate. An operator may be defined as “a symbol which represents a well-defined set of mathematical operations
to be carried out on a function (operand) that follows it.” Alternatively, an operator may be defined as “a rule of
changing one function in to another”. Symbolically.
O'
( O stands for a general operator. Circumflex is used over the letter to indicate that it is an operator) Note that
operators without their operands are meaningless. SIME CONVENTIONS IS USING OPERATORS :
(i) A B A B B A B A
The result of operation by a sum of two operators, on a functin is same as the sum of the results of operations of
individual operators on the function. Also, the addition of two
operators is commulative i.e. order of addition is immaterial : A B B A
(ii) Although addition (and subtraction) of operators is commutative, the product
of two operators may not be commutative always. A B B A and the result depends on
the order in which the operators operate. The product of two operation is defined as A B A B A ' ''
In the operation by A B , it is the operator B that operates first and the result is
next operated upon by A to give the final result. In a product, the operators are assumed
to operate successilvely, beginning with the operator immediately on the left of the function i.e. beginning with the
operator on the extreme right in the operator product we gradually work leftward. This sequence in operations is
important since as said earlier,
A B B A i.e. multiplication is not commulative.
Example : Let A be x (multiplication by x )
and B be d/dx (taking first dervative with respect x) consider a function, f ( x ) x 2
d $ 2 d 22
A B f ( x ) x . x x ( x ) x (2 x ) 2 x
dx dx
d 2 d 2 d 32
BAf
(
x

)
.
x
.
x
(x)

dx dx x x dx 3 x
A B f ( x ) B A f ( x ) ( A B B A ) f ( x ) x 2 f (x ) Lifting the fuction,
(ABBA)1
( A B B A ) is called the commutator of the operators A and B and is represented
as A , B . The value of the commutator is different for different pairs of operators.
If A , B 0 i.e. A B B A the operators A and B are said to commute with
each other and the order of operations is unimportant.
Note that the commutator of two operators is itself an operator. If the commutator is zero. (a null operator), it will
annihilate its operand. Note also the deep physical meaning of the commutation, behaviour of operators. if two
operators commute then the variable corresponding to them can be simultaneously determined with complete
precision.
(Does x commute with Px )
(iii) LINEAR OPERATOR
An operator A is said to be linear if the result of operation of A on a sum of functions is same as the results of
operation of A on individual functions.
i.e., A f ( x ) g ( x ) A f ( x ) A g ( x )
or more generally
Aaf(x)bg(x)aAf(x)bAg(x)
(a, b are constants)

Note that not all operators are linear. For example, d/dx is linear but ( )2 or is not linear.
(iv) HERMITIAN OPERATOR
All operators that we use in quantum mechanics are Hemitian. The Hermiticity of an operator assures real values
of the associated variable. The definition of a Hermitian operator is a little difficult to grasp. An operator A is said
to be Hemitian if, for any well behaved functions.
m and n
m
A
n
d
n
A
*
*
m
d
*nAmd
all space all space all space
*
using Dirac bracket notation,

m|A|n

*
n|A|m

(Only the subscripts are used to designate the functions) or A mn A * nm

(v) EIGENVALUE EQUATION
When an operator operates on a function, the function in general, changes into a new function (definition of an
operator). However, it is interesting to observe that between certain operators and operands a special relationship
exists such that Aa (a is a constant)
That is, when the operator operates on the state function the function is not changed except that it gets multiplied
by a constant. when this happens, the function is said to be an eigenfunction of the operator and the constant
multiplier is said to be the eigenvalue of the operator with respect to that particular function. This interesting
relationship embodied in above equation is of great interest in quantum mechanics and is known as the eigenvalue
equation.

Exercise : Show that e ax is an eigenfunction of d / dx . What is the

eigenvalue ?
d e ax a e ax (a = constant) dx
Exercise : Find out if
e ax is an eigenfunction ofd belonging to the eigenvalue a.dx
ax 2 is an eigenfunction of d e
. dx
d e ax 2 a . e ax 2 . 2 x 2 a x . e ax 2

dx

constant x . e ax 2
e ax 2 is not an eigenfunction of d .dx
The eigenvalue equation has a deep significance. It is the counterpart of experimental
measurement in classical theory. If Aa , then the property A associated with the
operator A is well-defined, i.e., known with complete certainty. Its value is a in the particular state . The eigenvalue
thus represents the precise result of determination of the variable associated with the operator in the state described
by the eigenfunction (eigenstate ).
(vii) IMPORTANT THEOREMS ON HERMITIAN OPERATION
THEORAM-1 : The eigenvalues of Hermitian operators are real. Proof : Let be an eigenfunction of an operator
A with an eigenvalue a. A a ------(1) Taking the complex conjugate of (1)
* * a * * ------(2)A
Multiply (1) on the left by * and intergrate
* A d a * d ------(3) Similarly multiply (2) on the left by and integrate
*
A * d a * * d ------(4) If operator A is hermitian, the left hand sides of equation (3) and (4) must be equal (definition)
*
*AdA*d
The right hand sides of (3) and (4) must also be equal, i.e.
a*da**d
a a * (Note : * * )
This can be true only if a is real.
THEOREM - 2 : Eigenfunctions blonging to different eigenvalues of a Hermitian operator are orthogonal.
Before we can tak up the proof of this theorem, we must understand what are
“orthogonal” functions. So far we have said that an acceptable must be normalized to unity.
i.e, * d 1
ORTHOGONAL FUNCTIONS :
If 1 ( x ) and 2 ( x ) have the property that
b
*2 ( x ) 1 ( x ) dx 0
a

for a certain integral (a, b) then 1 ( x ) and 2 ( x ) are said to be “orthogonal” in this interval (a, b).
If we have a whole set of functions i ( x ) i.e.
( x ) ,2 ( x ) , .................. such that for any pair of functions1
( x ) and j ( x ) (i j )i
b*
i ( x ) j ( x ) dx 0 ( for i j ) a
i.e. such that every pair of functions in the set is orthogonal in the interval (a, b), then the set is said to be an
orthogonal set for (a, b). If, in addition, the functions i ( x ) are normalized individually, i.e.
b
*
( for all i ) a
i ( x ) i ( x ) dx 1
the set is called an orthonormality set for (a,b). Thus the condition for individually
orthonormality and pair-wise orthogonal) is
b
* (x) (x)
i j
dx ij a

ijis ‘cronecker delta’ with the properties that = 1 if i = jij

= 0 if i j
The advantage of having a complete orthonormal set of functions i for a system is that any arbitrary state of the
system can always be completely expressed as a linear combination of the members of the complete orthonormal
set.
c 1 1 c 2 2 ..................... c i ------- (1) i
( x ) and c 1 are constantsi i
Multiply (1) by * ( x ) and integraten
* dx c * * *
n 1 n 1 dx c 2 n 2 dx ................. c n n n dx +.... ------- (2) All integrals on the right hand side of (2) vanish
except
c
*
n n n dx c n (Qn normalized )
c n * n dx
------- (3) In the same way all c i ' s can be determined if the expansion is valid. If i are chosen to be
eigenfunctions of F , i.e.
F i f i i ------- (4) then F c 1 F 1 c 2 F 2 .................. ------- (5) Multiply (5) on the left by
* c * * c * * .................
1 1 22
and integrate
* F dx ( c 1* 1* c 2* 2 * ............) F (c
1 1 c 2 2 ......) dx
c * F 1 dx c 1* c 2 1* F 2 dx ............ ------- (6)1* c 1
All terms of the type a m * a n m * F n dx on the right hand side of (6) must vanish due to the orthogonality of m andn
(m n). The only terms remaining are those with m = n, e.g.
c n * c n n F n dx c n * c n f n n * n dx
c n 2 f n ------- (7)
*
F
dx
F c ------- (8) F 1
c 2 f 2 2 f ............ In (8), c P is the probability or weight factor of the eigenvalue f .
1 2 2 i
ii
FPf ------- (9)
i ii
Thus the expectation value of F (i.e. the mean value of F) is the sum of the probability - weighted eigenvalues f i .
Proof of Theorem-2 :
Let 1 and 2 be the eigenfunctions of the Hermitian operator A belonging to the eigenvalues a 1 and a 2 .
respectively. A 1 a 1 1 ------- (1) A 2 a 2 2 ------- (2)

From (1) :2 * A 1 d a 1 2 * 1 d ------- (3)

Since the operator A is Hermitian,
*
* A 1 d 1 A 2* d 2
a1
a 2 1 2 * dt ( a 2 * a 2 ) ------- (4) 2* 1 d a 2 2* 1 d
a 1 a 2 2* 1 d 0 ------- (5) If a 1 a 2 (i.e. 1 and 2 belong to different eigenvalues i.e. are non-degenerate), then
2* 1 d 0
1 and 2 must be orthogonal.
Schmidt orthogonalization :
If a 1 a 2 in (5) (i.e. 1 and 2 belong to the same eigenvalue, i.e., are degenerate)
then since a 1 a 2 0 , 2* 1 d may or may not be zero i.e. 1 and 2 are not necessarily orthogonal. However a set of
orthogonal fuctions can always be found.
Let a 1 a 2 a
A1a1
A2a2

Let 2* 1 d b 0 ------- (6) consider2 '2 b 1 ------- (7) * d b * d

21 21 1
2* 1 d b 1* 1 d
bb
=0
Thus and* are orthogonal.1 2
A'AbAbA
22 1 21
a2ab1
aba'
212
Thus the linear combination 2 ' is an eigenfunction of A and belongs to the same eigenvalue a as does 2 .
(ix) HOW TO CONSTRUCT OPERATORS ?
An operator is the quantum mechanical device of meauring a variable and so we need to know the operator
appropriate to a given variable. These operators are constructed according to the following prescription :
Step : 1 Begin with the classical mathematical expression for the variable of interest and express it in terms of
coordinates and momenta of the system.
Step : 2 Make the following replacement :
a. Leave time and all other coordinates as they are.
x x (operation is multiplication by x)
q q (multiplication by q)
b. Replace all components of momenta, pq i by
i
H
q
HHh/2

iiqi

Note that ( i ) if the variable is some function of coordinates and momenta, then. the operator is the same function
of the corresponding operators. e.g. the z-component of angular momentum is defined as
Lz x P y y P x
The corresponding operator will be
$$H$H
Lzx i y
yix
$$
i H xy
yx
(ii) If the function is such that the order of factors is important, then, the operator must be constructed so that it is
Hermitian.
Examples : 1 Kinetic energy of a particle (T) :
2 p 2 1 Px 2 Py 2 Pz 2 1
T mv 2 (mv )
2 2m 2m 2m
1TiHiHiHiHiHiH

2m x x y y z z
H 2 2 22

2mx2y2z2
H2 2
2m
2 is called the Laplacian operator.

2 222
x2y2 z 2 TOTAL ENERGY (E) OF A SYSTEM
Total energy is the single most important peoperty of a system in which we shall be interested. The corresponding
operator is called the Hamiltonian operator or just the Hamiltonian, H .
Sinlge particle system :
E T V (V is the potential energy)
E
1 Px 2 Py 2 Pz 2 V ( xyz )
2m
This is the classical Hamilton’s function from which the corresponding operator derives its name.
H T V H2 2 V (x , y , z )2 m
Two particles (identical) system : ( m 1 m 2 m ) E 1 m v 1 2 1 m v 2 2 V P 2 / 2 m P 2 / 2m V
2 21 2
2 12 2 V (x y z x y z )H H
2 1 1 1 2 2 2
2m
(Note ) V here is the potential energy of the whole system) If the two particles are not indentical m 1 m 2 :
H H2 1 21 1 2 V m 2
21 m 2
We shall be generally concerned wih electronic Hamiltonians for atomic and molecular systems where all particles
of interest are electrons (indentical). N-electron system :
ETiV
i
H
H
2
i2V (q i ) ................ q x , y , z i 1,........N 2 m i
Hydrogen atom : (z = 1)

-ve
V ( r )e 2 r r
+ve
H
H2 2 2m Helium atom : (z = 2)
r1

r2 V
V (r )
2e 2 r
1
A r attraction of e 1 by 12 B the nucleus
2e 2
r
2
attraction of e 2 by the

nucleus
e2
r
12
repulsing between e 1 and e 2

2
H 2H m 1 2 2 2 V
Carbon atom : (z = 6)
There are six e outside the nucleus of charge +6e. The total P.E. (v ) comprises six

attractive terms of the type 6 e 2 , one for each electron and fifteen interelectronic
repulsive r i
2e
terms of the type r ij , one for each distinct repelling pair of electrons. Thus :
V
6e 2 6e 2 6e 2 6e 2 6e 2 6e 2
r r r r r r 1 2 3 4 56
2e2e2e2e2e
r r repulsion of
12 r 13 14 r 15 r 16
e 1 by all other e'se2e2e2e2
r r r r repulsion of
23 24 25 26
2e2e2e

r r r repulsion of
34 35 36
2e2e

r r repulsion of
45 46 e 2
r repulsion of
56
H 2 6 6 16 1
e 2 by all other e ' s
e 3 by all other e ' s
e 4 by all other e ' s e 5 by all other e ' s

Hi26e2e2r
2m i 1 i 1 r i i j ij
In general for an atom with atomic number Z,
2 zz 1 e 21 H H z

2Ze2r
i
2m i 1 i 1 r i i j ij
Exercise : State explicitly the potential function and hence write the Hamiltonian operators for (i) Lithium atom (z
= 3) (ii) Oxygen atom (z = 8) and (iii) Hydrogen molecule, H2 .
THIRD POSTULATES OF QUANTUM MECHANICS
SCHRODINGER EQUATION:
We have said earlier that is a rich source of information about the state and have described how operators can serve
to extract information contained in . So far we have said nothing about the source of this powerful quantity: How
to get this ? This question is answered in Postulate 3 which states:
The possible state functions of a system are the solution of the differential equation.
HiH
t
This equation, known as the time-dependent Schrodinger equation, is the fundamental equation of motion in
quantum mechanics. It describes how develops with time. It must be mentioned here that, although it is easy to
write the Schrodinger equation for any system, it is very difficult to solve it exactly for most of the systems. In fact
it has been solved exactly for only the one-electron systems (hydrogen atom and hydrogen-like ions). For all other
systems. only the approximate solutions are obtained using standard approximation methods such as the variation
principle and the perturbation methods.
Let us practice writing Schrodinger equation using simple cases.

Chapter-3
QUNTUM MECHANICS OF SIMPLE SYSTEM WITH THE CONSTANT POTENTIAL ENERGY :
QUANTUM MECHANICS OF SIMPLE SYSTEMS
PARTICLES IN A BOX PROBLEMS
We shall now apply the principles discussed above to some simple artificial systems The most obvious virtue of
these elementary applications of Schrodinger equation is their simplicity such that without bringing in excessive
mathematics it is possible to obtain exact solutions. At the same time, these applications very elagently illustrate
many of the fundamental aspects such as quantization, degeneracy etc. of the quantum theory. Again, the results
are of real chemical inerest since these artificial systems serve as convenient models for situations of chemical
interest.
FREE PARTICLE :
This is a trivial case but its discussion can lead to better appreciation of particle
in a box problem to follow.
A free particle is a particle moving in a constant potential field with no coordinate restriction.
V = constant = 0 (arbitrarily)
Assume a linear system i.e., V(x) - 0. Our interest is to find the wave functions and energy for this free particles.
H2 d 2 H 2m dx 2

Schrodinger equation will be

H2 d 2
2m dx 2 E
d 2 2m E
d2
d
2 2m E Px 2
k 2 0 Where k 2
dx 2 H 2 H We can easily guess the solutions which could be
( x ) A sin kx ( x ) A cos kx
(x)A
.e ikx
(i) Note that there is no restriction on k and hence on E,
i.e. the energy of a free particle is not quantized.
(ii)* A * A e ikx . e ikx A * A constant so that
all positions are equally probable for a free particle i.e. Position is uncertain.
(iii) Let us obtain Px.
Hd A e ikx P x i dx
H k . Ae ikx H k
us an eigenfunction of Px with the eigenvalue hk .
exact value of Px H k

2m E

which is the classical result.

PARTICLE IN A ONE-DIMENSIONAL (LINEAR) BOX
Since the position of a free particle is completely uncertain let us confine it between
x = 0 and x = L x so that we know for certain that the particle exists somewhere between these limits. This problem
is called the “particle in the box.” It corresponds to the potential function .
V ( x ) V ( x ) const 0 V ( x ) x 0 for x 0 0 x Lx for x Lx V ( x ) 0 0 x Lx ( x ) 0 ( x ) finite ( x ) 0 x Lx
So that the particle is constrained within two infinite potential barriers.
For the infinite potential region outside the box (x < 0 and x > Lx) it can be shown that the only acceptable
solution is ( x ) 0 i.e. the particle cannot get out of the box.
For the inside region (0 < x < Lx), V(x) = and the Schrodinger equation is same as that for a free particle
d 2 2mE Px 2
2 k 2 0 where k 2
dxH2H
The solution ( x ) must be “well-behaved”. Since ( x ) 0 everywhere outside, continuity will require that ( x )
vanishes at the walls (x = 0 and x = Lx ) Thus the boundary conditions on acceptable solutions are :
(0) 0
( Lx ) 0------(1)
i.e. ( x ) 0 at x 0 and x Lx
Equatio (1) has a general solution
( x ) A sin kx B cos kx ------(2) Applying the boundary conditions,
(0) A sin 0 B cos 0 B 0
( x ) A sin kx
Simularly, ( Lx ) A sin k Lx 0
A 0, k Lx n x ------(3) Where n x 1, 2, 3,..............
nx k
L
n
( x ) A sin nx x
x Lx ------(4)
EVALUATION A:
The constant A in (4) can be obtained by applying the normalzation condition.
Lx
* ( x ) nx ( x ) dx 1
nx
0
Lx
A sin nx x . A sinnx x dx 1 0 Lx Lx
2 1 cos 2 )
Use sin (1
2
Lx nx x dx 1A 2 sin 2 Lx 0
A
2 Lx Lx
dx cos 2 nx x dx 1 20 0 Lx

A 2 1 Lx 0 1
21
A2
Lx 1
22A2
Lx
A 2 n x 1, 2,3,.................... -------(5)
ZERO POINT ENERGY (ZPE) :
There is no energy state corresponding to the particle at rest with KE = 0. Why ? for E - 0, = 0 everywhere in the
box. The box is empty !
More convincing argument derives from the uncertainty principle. The best that we can say is that the particle is
located some where in the box 0 x Lx . x Lx
If E 0, Px 0 and Px 0 .
x . Px 0
This violetes the uncertainty principle.
The lowest energy corresponds to the lowest value of n x ( 1) and is E 1 h 2 / 8m L 2 x E 0
called the zero point energy (ZPE). Zero point energies are characteristic of bound systems.
PARTICLE IN THREE DIMENSIONAL CUBIC BOX
x
v = vx = 0 v =
vy = 0 A x vz = o
b
y (a b c)
The schrodinger equation for a constant- energy in a field- free cubic box of side a in which V is zero for any value
of x, y, or z between zero and a but infinite outside these limits, This is

(E- V)
= 0 ……………… ( I )
+

E
= 0 …………………….. ( II) ( v = 0 )
When is a function of three independent variable x, y and z. It can be shown to be a product of three function
separately dependent on the same variable. i.e. sTZ\U
lJW[I
G[[ +6[ lNXFDF\ +6 :JT\+ TZ\UlJW[IMGF U]6FSFZ :J~5[ NXF"JL XSFIPf
( x, y, z) =
x
y
z ……………… (III)
(x) is the function of x and independent y & z,
(y) is the function of y and independent from x and y.
i.e.

=
y)
z)

=
x)
z)

iv

=
x)
y)

put the value of (III) & (IV) in Eq. (II)

y)
z)

+
x)
z)

+
x)

y) +

x)
y)
z)
…………… (V) Divide by
(x),
y), & z) Four steps in Eq. (vi) 4th step is constant if change the value of 1st step by keeping constant the
2nd rd
& 3 steps.
i.e.
x
 +

=0
x

= 0 VII
x

=0
Multiply 1st eq by
(x), 2nd by
(y) and 3rd by
(z) in Eq. – VII

(x) = 0

(y) = 0VII

(z) = 0
Eq- VIII are the same like particle in dimensional box, therefore the normalized wave functions and the Equ. of
energy are
(i) Normalized wave functions
(x) =

sin
x
(y) =

sin
y
(z) =

sin
z ………………….. (IX)
(x,y,z) =

sin
x. sin
y. sin
z
 (ii) Energy : E = Ex + Ey + Ez E=

E=

[ n2 x + n2 y + n2 z]
DEGERENCY
Energy Equation for three dimensional cubic box is E =

] ----------------- ( I )
For cubic box s;D3Gf a = b = c
E=

[ n2 x + n2 y + n2
z] ---------------( II)
Put the value n= 0 in Eq- (2) i.e. nx = ny = nz = 0 there for E = 0 put the value n=0 in Normalization wave function.
So
become 0 (
2 = 0 ) means probalility to finding the
in box is zero i.e. There is no particle in box. But particle is in box it is real fact. So value of (
2 = 0 ) is not possible & also n 0 ( n = 0 CM. XS[ GCÄf

So, minimum energy level sGLRL SJMg8D VJ:YFf nx = ny = nz = 1 put the value of this sets of Quantum
Numbers in Eq = II
E=

( 12 + 12 + 12 )
E=

Here, for this energy level, only one set of Quantum number (1,1,1). So we said this energy level is non-
degenerate energy level.
Then for higher energy level, we get the sets of quantum numbers are (1) nx =2, ny =1, nz = 1
(2) nx =1, ny =2, nz = 1
(3) nx =1, ny =1, nz = 2
For this energy levels
E=

After this position, Also we get three sets of Quantum numbers, which have the same energy. s+6[I SJMg8D
V\SMGL XlST ;DFG CMI K[Pf and this energy energy levels are try- deqenerate energy levels.
Then higher energy levels are as under.
E5 =

(2,2,2)_______________ Non – degenerate

E4 =

(3,1,1) (1,3,1) (1,1,3) _ Try – degenerate

E3 =

(2,2,1) (2,1,2) (1,2,2) _ Try – degenerate

E2 =

(2,1,1) (1,2,1) (1,1,2) _ Try – degenerate

E1 =

(1,1,1) Zero Point Energy (ZPE) _ Try – degenerate

______________________________________________ Quantum numbers (Energy)
Degeneracy s;DXlST56]f of energy levels is depend on the symmetry of cubic box. ( a=b=c). if (a b c) decrease
the degeneracy and increased the energy levels. One Dimensional Box
Put the value of K in Eq – (6)
= Asin (
) x -------------- (7)
Eq- ( 7) shows the wave function of
in one dimensional box
Energy :- K2 =

(
)
2 =

( where K =
)

E=

E=

( Energy Equation for the particle in dimensional box)

CONSERVATIVE SYSTEM :
By a conservative system we mean any isolated system, not acted upon by external forces (V depends only on
position coordinates) and with no internal dissipative forces, whose total energy (E = T + V) remains constant with
time. Such a system exists
in quantized stationary states which are described by state functions of a special form. ( x , t ) ( x ) . (t )
Space
Time
part part
Which permits the SEPARATION OF VARIABLES so that the Schrodinger equation can be split into two
independent equations.
Hi H
t -----(1) Assume ( q , t ) ( q ). (t ) -----(2) H i H t
H i Ht
H i H . -----(3) t

The left hand side of (3) depends on the position or space coordinates q (i.e., x y z) while the right hand side
depends only on t. Since x, y, z are independent of t, eq. (3) can be true only if the two sides separately
equal some constant, say E. H E or H E ------(4)
iH
and . E ------(5)t
We see that assumption (1) has enabled us to separate the space and the time parts of the time-dependent
Schrodinger equation.
Equation (5) is easily solved. It can be rewritten as

iEt
H
Upon integration,
iEt
H
(t ) e iEt / H ------(6) Equation (4) is the familiar time independent Schrodinger equation :
HE . This is an eigenvalue equation for the Hemiltonian operator (corresponding to the total energy) and the
eigenvalue E represents the energy of the stationary state (We were foresighted to choose E to represent the
separation constant !)
In general : H i E i i ------(7) Where i represents the whole set of eigenstates and E i the corresponding energy
levels. Each member of i corresponds to a particular solution of the form. ( q i , t ) i ( q i ) . exp. i E i t / H ------(8)i
with H i E i i ------(9) the allowed eigenstates i .
i (i , t ) i ( i ) . exp . ( i E t / H) ------(10)
i
with H i E i i ------(11) Consider now the probability of observing the system in any of the allowed eigenstates,
i
*
i
i
* iE t / H . e * . i e i E t / H ii

ii

The probability distribution is independent of time. Each eigenstate is unique and rightly are these eigenstates
called the stationary states. We will summarize the above discussion and put it as a part of P.3.
ORTHOGONALITY :
consider n and m with n m ( n m ) .
Lx

n m dx 0
L
2 x n x sinm x
dx Lx sin
0 Lx Lx
Use :
sin
A
sin
B
1 cos ( A B ) cos ( A B )
2
L
x
x
dx
cos (
n
m
)
x dx Lx
2
1
Lx
cos ( n m ) 2 0 Lx Lx
0L
1 Lx sin ( n m ) x Lx sin
( n m )x x
Lx ( n m ) Lx ( n m ) Lx 0 = 0 m and n (m n)are orthogonal.
EIGENVALUES : ENERGY LEVELS
Recall the condition (eq. (4)) obtained on imposing the boundary condition. k L x n x
Px.Ln
Hx x
H Px n .
x
2L x
H We find that only discrete, special values of P x are permitted ! P x can be
2L x or
any integral multiple of it. In other words. Px and as a consequence the energy of the particle is quantized.

E
P
2
x
nx2m
E n 2 H2
nxx 2
8m L x
This is in contrast to the free particle without any constraint. Thus quantization is a consequence of boundary
conditions imposed,

E
Alternative Method for n x :
This is the usual method of calculating energy corresponding to a state function. We have H n E n n
*H*EE*

nnnn n nn
Integrating both sides and rearranging.
En * H n d /* d n n n
* n H n d if n is normalized Using (10) with the particle in a box function
nx : H
2
E 2Lx n x x d 2
nx x dx Lx Lx 2m dx Lx
nx si n 2 sin 0

H2 n 2 2 n x x 2m . x .sin Lx x 2
n2x
L
2 H2
. Lx 2 2 n x x dx 2mL 2 Lx sin LX
x0
Lx
n
*
ndx 10
x x
(v) Other properties of the system :
(a) Momentum Px in the ground state, E1 ,
H d The operator P x is
i dx . It can be shown that 1 is not an eigenfunction of P x .
Px H d

2 sinx 1 L i dx L x x
H

2 .x
cos x
i L x L x L x Therefore, measurement of Px will give a distribution of results. We cannot have exact knowledge of
Px. However, we can determine the mean value of Px from
Lx
P x P x 1 P x 1 dx (1 is normalized )
0
xHdx
Px
2 Lx sin Lidx sin L dx L
x 0 xx
2 x Lx x cosx dx
LL x i sin.H

x0LxLx
Use : sin 2 = 2 sin cos
h 1 Lx 2 x
iL
2 . 2 sin
0
L dx
xx
h L x Lx
x

2cos 2
2i L x 2 Lx 0
 H L x L xP 2
iLx22

Px

2 in the lowest state, . The operator of interest is H2 d / dx 2 .Consider P

1 x
H
2
d
221 H 2
dx 2 1 . 2 Lx
is an eigenfunction of P 2 with an eigenvalue.1 x
H
2
.
2
2 h2
L
x or4 L 2 x
. Therefore, a series of measurements on identical system will
always give a precise result (eigenvalue). P 2 ( state 1) h 2 2mE x 4 L 2 1
x
P x ( state 1)

2mE 1

But

Px

0
This interesting dilemma is resolved if we remember that Px represents the average of a large number of
measurements of Px on identical sytem. A single measurement will
give2 m E 1

or

2mE 1 and in a series of measurements, 2mE 1 will be obtained as

 m- any times as is obtained. 2mE 1 so that average is zero. We do not know in advance

whether an expt. would give 2mE 1

or 2mE 1

uncertainty in P x P x 2. 2mE 1
2.
H
.
hLxLx

L
Maximum incertainty in position,x x
. P x L . h h ( for state n 1)x x Lx
.P
In general x x nh
x.Pxh
This is Heisenberg’s undertainty principle.
(b) Consider the position x of the particle in the lowest state. The operator is
x$
(multiplication by x)
Lx x dx

2 x sin 2 xL0L
xx
sin2 1 1 cos 2
2
2
.
1
Lx
x 1 cos 2 x
dx
L x 20 L x
Lx 2 x 2
Now x . dx x Lx
0 20 2
Lx 2 xLx Lx sin2 x x cos dx u dv if u x v L
0 x02Lx
Lx uv v du 0

LLx L
x
.
x2x dx 2 sin2 x x
L sinL 2
x0x
x
.
L
x
sin
2
x
2 2 x Lx Lx cos
L 2 L 42
xx 0
2 222
0 Lx 0 Lx Lx Lx 0 2 42 42 42 4

$
It can be shown that x

is independent of n, but $ 2Lxx 2 2 n x

sin L dx
x

xL

0x
L 32 x1

3 2n 2 2
(c) Probability of finding the particle between x and x + dx is 2 dx . Using this we
can find the probability of finding the particle between x = 0 and x = 1/4 Lx in the ground state.
x /4 x
0L
0
21 dx 2
sin dx
x
2 Lx
L
1x / 4 2x dxL 1 cos
x0Lx
LL
1 x /4 x /42 x dx L dx cos
xLx
00
L
1x Lx sin 2 x x / 4 L
x2Lx01LL
xx (0 0)
Lx42
1 1 0.25 0.16 0.09 Q 1 0.32 4 2

(VI) Particle-in-a-box serves as a convenient model for several systems of interest e.g. e
in a metal wire, - electrons in linear conjugated molecules etc. It is possible to predict electronic spectra of
conjugated polyenes.
The -electrons are delocalized over the entire chain and may be regarded as particles in a one-dimensional box,
chain of conjugated C atoms of length Nd where N
is no. of C atoms and d c c 1 d d c c 2
n 2 h 2 mN 2 d 2 ; A sinn x En
8 Nd
It is to be remembered that N - electros in the lowest state, fill the lowest N/ 2 levels (two in each level). Thus,
absorption of energy would promote e from level with
n N to n 1 N 1
22
E
hv
E
N
1
EN
22
N
1
h 2 2 d 2 8mN h 2
hv 2 d 2 8mN

v 1 i.e. frequency of absorption should be inversely propotional toN

chain length. This is borne out by the following data for polymers.
o

Compund N v ( cm 1 ) A
Ethylme 2 61500 1625
Butadiene 4 46080 2170
Hexatriene 6 39750 2510
consequence of the symmetry properties of the system .

Chapter -4 SYSTEM WHERE THE POTENTIAL ENERGY IS NOT CONSTANT :

HYDROGEN ATOM :
(i) One electron problem : Hydrogen atom and hydrogen-like ions (He+, Li2+ etc)
are the siplest of the chemical system with just a single electron outside the nucleus of charge + Ze. These are the
only species for which the Schrodinger equation can be solved for EXACT SOLUTIONS. These solutions are
called HYDROGENIC or ONEELECTRON WAVE FUNCTIONS (aromic orbitals); these from the basis fpr
obtaining approximate solutions for more complex systems.
(ii) Special case of a two-body problem : The two particles the molecules and the electron - move about eacth
other and interact electrostatically, the inter-action epending on the distance of separation, r

V ( r )Ze 2
r
The mition of the relatively much heavier nucleus can be ignored (BornOppenheimer approximation) and problem
reduced to motion of electron with reduced mass relative to the centre of mass of the system,
m
.e

m
N m
N
me
By virtue of very (apherioally symmetric) between proton and
large difference of messes electron
m P 1846. m e the centre of mass practically coincides with the nucleus and
thereforewe are justified in regarding the electron in these systems moving about a stationary nucleus fixed at the
origin. Again
QmPme,me
Since the potential has a spherical symetry, the problem may be regarded as a CENTRAL FIELD PROBLEM
Ignoring the nuclear motion (translational part) of the problem, the Schrodinger
equation describing the internal motion of the hydrogen electron relative to the stationary proton can be writting
.
H
22V(r)E
2
Where
V (r )e 2
r (hydrogen)
Ze
2 (hydrogen-like-ion)

r
Solution of (2) will provide information about the possible energy states and spatial
distribution of the hydrogen electron. Eq. (2) is a three-variable equation which has been
e2
privents the straight separation of x, y, r

( xyz ) x ( x ).y ( y ).z ( z ) (r involves x, y, z , being related as r 2 = x 2 + y 2 + z 2 )

However, remembering that V(r) represents a centrosymmetric (spherical) potential
field, it seems logical to transform eq. (2) into spherical polar coordinates ( r , , ) where r becomes a single
coordinate and
needs no separation.
solved by separating the variables. V (r )
and z by writting.
r : distance of the point from the origin or the length of the line joining the point with the origin (OP)
0 r : angle between the line (OP) joining the pont to the origin and +Z axix : angle between the projection of the
line OP in the XY plane and +X axis. 0 2
The relationship between cartesian coordinates and polar coordinates are :
x = r sin cos r x 2 y 2 z 2 1/ 2
1
y = r sin
sin
tan
(x
2y2)2z
z = r cos tan y x
d dx . dy .dz (cartesian coordinates)
r 2 sin or d d (polar coordination)
222
2
2 2 2 (Cartesian coordination) xyz
1 2 1 1 r sin 2 sin2 2 r
2
x
t
r
2
r sin
Equation (2) upon transformation into polar coordinates become
2
12 1 1
r sin
2
r 2 r r r 2 sin r 2 sin2
82 E V (r ) 0
h2
r
Separation of Variables :
Assume : r R (r ) . ( ) . ( )
Substitute (4) in (3)
1 2 1r R sin R

r 2 r r r 2 sin
1282
r 2 sin2 2 REVR0
h2
r
2
R R sin R 2 2 sin2 2 r 2 r r r 2 sin r
82
h2EVR0
Devide by R 1r 2 R 1sin 12 r 2 sin2 2 R r 2 r r r 2 sin
82EV0h2
multiply by r 2 sin2 sin2 r 2 R sin 12 R r r 2 82 r 2 sin2 E V 0
2
1
222
or ,2 m 2 02 m
sin2 r 2 R sin sin m 2 82 r 2 sin 2 E V 0
and R r 2 r h 2
Devide (6) by sin and rearrange
1 r 2 R 8 2 r 2 E V 1 sin m 2 0 R r r h 2 sin sin2
1 depend on r depend on
2 r 2 E V (r )r 2 R 8
R r r h 2 r 2 R R 82 r 2 E V R 0
or r r h 2
1m2
sin sin2 or ,
sin
1m2
sin 0
sin sin2
Equations (5), (7) and (8) each depends on only one variable. Thus we have
separated the variables and resolved the total three-variable eqn. (3) into three independent
Note : (i) Energy of the system depends only on r but complete
wave functions
will require solving all three equations.
(ii) Although different two-particle systems will differ in their energy state and radial properties, they will have
similar angular properties of their wave functions.
(iii) We shall consider the three eqns. in the order
1. eqn. 2. eqn. 3. R ean. To be more explicit we shall first find the eqn.has acceptable solutions only for certain
values of m. We shall introduce these values of m into eqn. and find that eqn. has acceptable solutions only for
certain value of
.Introducing these values of into R eqn. we shall find that the acceptable solutions of R eqn. correspond to only
certain value of E which constitute the allowed energy states of the system.
(1) EQUATION
2

2 m20
The form of this eqn. is quite familiar to us. In fact, we have already discussed this eqn. and its solutions in some
detail.
A satisfactory soln. of the eqn. i s

m ( ) A e im
In order that the solution is acceptable, it must be well-behaved. One of the well0behaved requirements is that the
function must remain invariant on identity rotation. (i.e. complete rotation through 2 )

m ( )m 2

A e im A e im 2 A
e im . e 2 im e 2
im e 2 im 1

e 2 im e 2 im 2
2 cos 2 m 2 or cos 2 m 1
m 0, 1, 2, 3
Thus, for each numberical value of m (other than m = 0) there are two solutions of the form (9), one with positive
m and the other with nehative m.
Thus we find that solution of equation results in a restricted set of wave functions denoted by quantum nunber m
which from its allowed values may be indentified with the magnetic quantum number of the Bohr ommerfeild
theory.
The constant A in (9) may be obtained by using the normalization condition
2
*d1
mm
0

2 2 A * A e im e im d A * A d 0 0
A*A21
A
*AA21
2A

12
Choosing the positive number the set of well-behaved solutios of eqn. will be
m
(
)
1

2 e im m 0, 1, 2, ..................
The solutions we have discussed so far have been complex solution. For some
purpose, it is convenient to have alternative real solutions. These can be readily obtained
since if
m
A e im

m Ae im and are solutions of the eqn. then linear combinations

of these functions will also be the solutions. Thus for a given m , the sum and the difference of two complex
solutions will give
1
m ( ) cos m

1 sin m m ( )

For m=0, there is only one real solution.

The -solutions, except for m=0, are all complex. For obtaining them in real form, the two solutions corresponding
to the same m are linearly combined i.e. added and subtacted. For example.
N 1 1 1 cos
1

1 N 1 sin 1 1

Consider N 1 1 :
2* N1d1N1
110
2222
N * N 1* 1 d 1* 1 d 1* 1 d 1* 1 d1
0 0 00
Since 1 and 1 are individually normalized and as a pair orthigonal N * N 1 1 1
N
* NN212
N 12
Normalized linear combination is 11 12
1 . 1ei e i 2 2
1 . 1. 2 cos 2
1 . cos

Similarly, consider N 1 1
N .11 e 1 e 1 N .

2 . 2i sin 2
2i N sin .

Evaluate N by normalization
2 * 2
N N 2i2d1

sin
0
2
i
2 N * N . 12 2
2 d cos 2 d 1 2 0 0
2 sin 2 0

20 2 N * N 1 i .e . N * N N 2
1i22i
21
N

2 .i
N 1 1 1 sin

In general
1
1 cos m
1
m function 00 ( )
11 ( )
-11 ( )
1 sin m
SOME m ( ) FUNCTIONS in terms of
1
2
1ei 1 2
1
i
e
12
+22 ( )

1e 2 i 1 2
(
)
1e 12 2 i
22
(2) EQUATION :
1ddm2
sin 2 0
sin d d sin
The solutions to this eqn. are not obvious as in the case of eqn. is of a form familiar to mathematicians as the
Legendre’s equation for which solutions were wellknown long before the advent of Quantum mechanics. The
solutions are associated
Legendre functions generally denoted by P m cos . These have specfic functional form for givenr
values of l and m.
Eq. (8) may be written
1 d sin d m 2 sin d d sin2 0 taking the indicated derivative
22
d cos d m 0
d 2 sin d sin2
must be well-known in the interval 0 or 1 cos 1
Let us change the variable as
x cos
d sind ;d 2 sin2 d 2 cosd d d x d 2 dx 2 dx Substitute into 915) and simplify
22
sin2 d 2 cos d m 0 dx 2 dx sin2 or,
2dm2

1
x
2d
22x20
dx dx sin
The well-known associated Legendre’s equation is
1 x 2 d 2 2 xd 1 l 1 m 2 0 l 0,1, 2,3,............

dx 2 dx m 1 x 2
P
m ( x ) 1 x md
2P(x)
l dx m l

Where P (x ) is the Legendre’s polynomical of degree l .

l
P (x ) 1 d l 2 1 l x
l l l
l 2 1 dx
1
l d ll
2
l l dx l 1 x 2
1
P m ( x ) are orthogonal in the interval 1 x 1
l
and P m ( x ) m for m 1
l
Normalized assoc. legendre functions are
1l1mlm

d
lm l
(
x
)
2 l 1 22
ll
 . 1 x 2 1 x lm
21 2 1 m l dx
Our eqn. (18) becomes identical with the associated Legendre’s eqn. (19) if we put
1l1
and then the
Normalized
-solutions are given by (21). Since m enters -eqn. as m2 . lm ( ) l m ( )
solutions have the form
lim ( )
1l1
2 l 1 .
2l 1l

21
m l lm 2 l m
l
sin m d sin dxl m
For1 l ( )
1 l ()
11m1
l11i1
3. i 2 ll 12

1 1 sin
d 2sin2
2 d cos
sin2 1cos2 d
d cos 1 cos2 2 cos ;
()1

3 sin ( 2)
11 2 4
d 2 d cos2 1 cos2 2

3 sin
4
SOME l m ( ) FUNCTIONS
l m Function

or 1 0 0 00 ( ) 2 22
1 0 10 ( )6

cos2
13

sin 1 1 ( )2

2 020 ( )10 4 3 cos 2 1

1

sin cos2 1 ( )15 2

15 sin 2 2 2 ( )
4 2

Note that solution of eqn. introduces a new quantum number l (l = 0, 1, 2, 3, .......) which may be
indentified.
with the new azimuthal or orbital momentum quantum number of Boht
Sommerfeld theory, Also it restricts m to
m 0, 1, 2, .................., 1
(3) R-equation :
1 d dR R 2
2
2
r dr
E V ( r ) 0R 2 r 2dr r H
V(r)e2

r (hydrogen)

2
Z e r (hydrogen-like ion)
and 1(1 1) ; 1 0, 1, 2,...........
1
d
r
2
dR
l
(
l
1)
2
Ze 2
E

r 2 dr r
Introduce 2 2Edr r 2 H2 R 0

2 and Ze 2

2 HH

and change the variable r p : p 2 r

Eq. (27) becomes
d 2 R 2 dR l l 1 1R 02 2
dp p dp p 4 p R R ( p )
Eq. (29) has been solved by a POLYMINAL or POWER SERIES
METHOD and the solutions are the wellknown associated langerre polynomicals :
1p
R nl ( p ) N nl . G ( p ) . e
2
G ( p ) are related to (for given n and l ) assoc. Langurre polyminals as
2l1
G ( p ) pl . L n l ( p )
L s r ( p ) is defiend as
L s ( p ) ds L ( p )
r
dp
s
r
Where L r ( p ) is the Langurre polynomial of degree r given by
r
L
r
(
p
)
e
pd prep
r
dp
1p2l12R
nl ( p ) N nl . pl L n l ( p ) e N
The normalization factornl is given by
1
i2 2Z 3 n l 1
N
nl
na

0 2n n 1i
3
Note :
(i) while obtained well-known solutins R ( p ), turns out to be a non-zero positive integer and this may be identified
with the principal quantum number, n.
n 1, 2, 3,................., n 0 Also, the values of l are restricted as l 1, 2, ................. n 0
(ii) The familiar Bohr expression for quantized energy states of a hydrogen-like system follows at once from the
definition of
n on substitution for .
Let us construct R 10 ( r ) :
n1l0
L 11 ( p ) is required
L1(p)epdpep/
dp 1 p
L
1
(
p
)
dL
(p)
1 dp d 1 p dp
1

G(p)p

0 ( 1) 1
11
2
Z
3 oi 2 2 Z 3 12 Now
N
10 . 2a 0 2 1 i 3 a 0

We have seen that complete solution of the wave equation for well-behaved solns. introduces three quantum nos. n,
l, and m . These quantum nos. were arbitrarily introduced in the Bohr Somerfeld theory whereas in wave
mechanics they appear as a consequence of a few basic postulates of wave mechanics.
The total wave function descriing any state of H atom is, of course, the product of R, and functions
nlm ( r ) R nl ( r ) lm m ( )
R nl ( r ) Y lm ( )
sis referred to as the SPACE WAVE FUNCTION (ORBITAL) nlm
The complete hydrogen atom wave functions are listed below :
H-LIKE WAVE FUNCTION
npzr
2 a 0 K-SHELL
2 n =1 l =0 m =0
3
1Zae1s

0
K-SHELL 1
2
1 32 n =2 l =0 m =02 s 2 Z a 2e2
132 n =2 l =1 m =02 p 2 4 0
1 2 Z e cos
2 2 4

a
1
132
22 Z a0
0
n = 2 l = 1 m = 1 2 px 4 e 2 sin cos
1
22
13

2
Z

ae

2 py 2 sin cos 40
M-SHELL
n
=3
l
=2
m
=0
1
3s3Z

32
2
 3
a 27 18 2 e
810
32

n
=3
l
=1
m
=
0
3 pz
2

Zae 3 cos
81 0
32
n
=3
l
=1
m
=
1
3 px
2

Zae

3 sin cos

81 0
32

3 py
2

Zae 3 sin cos

81 0
n = 3 l = 2 m = 03 dz 2 3 1 6
Za322e

3cos2 1 81
2

Zae

sin cos cosn = 3 l = 1 m = 1

3
22
3 dxz 3
81 0
3
22
3 dyz 3
2

Zae

sin cos sin 81 0

1

2
Z
3
n
=3
l
=2
m
22
3 dx 2 ae
3 sin2 2 =
2
cos 810
1

2 Z
32 2
ae

sin
2 sin2
3 dxy 3 81 0
SCF METHOD SELF CONSISTENT FIELD METHOD : DRAWBACK OF HUCKEL
THEORY (LIMITATION)
The main limitation of Huckel theory was that, theory did not consideration of the repulsion energy
term

like which depends on the co-ordinate of both

. Due to this, the thory failed to explain the excited state phenomena. However in a closely related series
of molecules this neglet of
repulsion will be minimum and so gives statis factory results, (Hukels theory
repulsion )
In the self consistent field method a single
is treated as if it was moving in the presence of a central electrical field resulting from the average
charge distribution of the nucleus and the remaining
s. This is to estimate the potential energy function due to the nucleus and all of the
s.
The solution to the wave eqn. for the first
will give the average central field which can be used for the wave equation of the second
and so on this procedure gives improved wave function for the
untill no appreciable change is noted. At which point the field is set to be self-consistent.
For a system, the humiltoniam operator is expressed in atomic units as

=
(core) +
.................(1)
i & j represents
pair
=
repulsion term.
The first term
(core) determines the attraction energy of the core for teh
- electron, which is given by

..............(2)
(core) =

-
Where Za the nuclear charge on nucleus ria = the distance of an
" i "a from nucleas "a" st is subjected to the average field of an To evaluate
lets first take the case of 2
s.

(2) which occupies the molecular orbital i The average field is given by

(2) (
) dT2 ................(3)
 Since the
can exchange betn the
M.O. " i" & " j" this can be represented as
(2) j(2) (

) dT2 ................(4)
The eigen value eqn to be solved for an (1) in molecular orbital say " j" is given by
(core) +
(2

-
] j (1) = j j(1) .......(5)
Where,
i i(1) = { i2
(1) (
) dT2 } j(1)
i i(1) = { i(2) j (2) ( ) dT2 } j(1)
= coulomb operator
= Exchange operator
The L.H.S. of the eq-(2) is called as the effective Fock- operator (
) and the eigen value eqn is simply written as
FJ(1) =
j J(1)
i=
i i ..................... (6)
i = As in simple Huckel theory, the M.O. built up in the LCAO form as Cij j ....................(7)
Application of variation method leads to a set of secular equations the determinant of which can be written as
11 -S11 E 12 -S12 E 13 -S13 E
21 -S21 E 22 -S22 E 23 -S23 E = 0
------ ------- --------
----- ------- --------
i = F ii = <
i>
ij = Fij = <
j > .................(9)
sij = < i / j> In integral ij can be evaluated using the relationship
i = i (core) +
<ii/ii>+
qi < i i / j j > ..................(10)
Pij < i i / j j > ............(11) ij = ij (core) -
Here, qi = total
s density on atom " i "
Pij = Bond order i (core) andij (core) are given by the Expression.

i (core) = < j /
Hi (core) / j >, i = j
(core) = < i /
 Hi (core) / j >, i j ij
0. atom i being linked to atom j = 0, otherwise With the above Eqn (10) < i i / i i > describes the electron repulsion
between two s in the field of the same core and < i i / j j > in Eqn (11) between two s on the
neighbouring cores i and j with this eqns the cofficients of the secular diterminant is solved & finally the
density q & the bond order P are calculated.
These set of q & p values are used to calculated an improved set of & values and the process is continued until
consistency is achieved.
The self consistency formula of M.O. theory is based on may Hamiltonian developed " Roothan"
incorporating the
repulsion energy term
which depends on the co-ordinate of both
s which cannot be repleaced by a one
potential energy term. To calculate i & ij we should have the values of i (core) i.e. the one
centre repulsion term and ij i.e. the two centred
repulsion term to evaluate these two we have to adopt the ppp approximation
(PPP Apron i (core), ij (core))