A COMPREHENSIVE TEXT
FOR CHEMISTRY
KISHOR ARORA
Hal
GJIimalaya GJlublishingGJIouse
MUMBAI • NEW DELHI. NAG PUR • BENGALURU • HYDERABAD • CHENNAI • PUNE
LUCKNOW. AHMEDABAD. ERNAKULAM • BHUBANESWAR • INDORE. KOLKATA
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ISBN : 9788184889369
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Preface
Studies of matter and to get structural parameters and properties of it has been a question in
front of mankind since past. Several experiments and observations were made in this regard,
Several laws and theories were given for this purpose. These studies can be broadly divided into
studies based on classical mechanics and those based on quantum mechanics. Classical mechanics
which is based on Newton's law of motion, was not able to explain the behaviour and concept of
black body radiation. Due to inadequacy of classical mechanics, quantum mechanic~ was originated.
This mechanics is based on concept of quantization as explained by Max Planck, Need to study
this mechanics is obvious if one has to get the first hand knowledge of structure and properties of
material/matter.
This mechanics has been a part of curricula of physical sciences at undergraduate as well as
postgraduate level. The present book includes 14 chapters starting from inadequacy uf classical
mechanics and covers basic and fundamental concepts of quantum mechanics including concept
of quantization of translational, vibration, rotation and electronic energies, introduction to concepts
of angular momenta, approximate methods and their applications, concepts related to electron
spin, symmetry concepts and quantum mechanics and ultimately the book features the theories of
chemical bonding and use of computer softwares in,quantum mechanics. Author hopes that this
book will cover the syllabi and serve the purpose of students' pursuing their studies in chemistry
at undergraduate and postgraduate level in different universities. Suggestions for further
improvement are Invited.
Author
"This page is Intentionally Left Blank"
Acknowledgem.ents
On the occasion of publication of this book I wish to acknowledge with deep sense of
gratitude and indebtedness to all my teachers who framed me and shaped me as a faculty of
chemistry. I would like to mention a few names Prof. N.K. Ray. recipient of Dr. Shanti Swaroop
Bhatnagar award who taught me the subject during post graduate level. I am highly thankful to
Dr. R.K. Agarwal EditorinChief, Asian 1. chern. who has been an ideal for me since childhood
and who guided me for my research degree. I bow my head and stand beholden to all my
teachers.
I am also thankful to Dr. Archana Bhardwaj (Principal). Dr. Prabha Mehta (Head) and all my
colleagues of my college. I am also thankful to my research colleagues and I would like mention
the name of Dr. D. Kumar here who has been always supporting in nature to me in the subject.
My thanks are also due to CDAC and team of Pune llniversity vi::.., Prof. S.R. Gadre. Prof. S.P.
Gejji for supporting me with Quantum Chemical Packages/Softwares. I sincerely acknowledge
their contribution. I am also thankful to my research students who have supported me to carryout
research in the field.
Last but not the least I sincerely acknowledge the continuous support and efforts of my
parents Late Shri S.P. Arora and Smt. Swadesh Arora who have been always encouraging me
with full enthusiasm to come out with the best. I am also highly thankful to my family viz ... Mrs.
Reena Arora (wife), Ms. Yashaswina Arora (Daughter) and Master Chittin Arora (Son) for their
continuous understanding. My thanks are also due to Dhamija family viz .. Shri S.P. Dhamija
(Fatherinlaw), Mrs. Sheela Dhamija (Motherinlaw) Mr. Deepak Dhamija (Brotherinlaw).
Mrs. Simmi Dhamija (Sisterinlaw) and Master Vibhor Dhamija for their cooperation.
I would like to extend my gratitude to the readers of this book and their suggestions for
improvement are invited.
Author
"This page is Intentionally Left Blank"
CONTENTS
Section  1
I. Classical Mechanics and Origin of Quantum Mechanics 326
2. Fundamental Concepts of Quantum Mechanics 2744
Section  2
3. Quantization of Translation Energy 4762
4. Quantization of Vibration Energy 6371
5. Quantization of Rotation Energy 7282
6. Hydrogen Like Atoms 83100
Section  3
7. Introduction to Approximate Methods 103109
8. Variation Theorem and its Application 110118
9. Perturbation Method and its Application 119123
10. Introduction to Angular Momentum 124136
11. Electron Spin and Related Concepts 137152
Section  4
12. Concepts of Symmetry and Quantum Mechanics 155173
t 3. Theories of Chemical Bonding 174194
Section  5
t Introduction to use of Computers in Quantum Mechanics 197204
Bibliography 205207
Appendix 208
"This page is Intentionally Left Blank"
SECTION1
1. Classical Mechanics and Origin of Quantum Mechanics
2. Fundamental Concepts of Quantum Mechanics
"This page is Intentionally Left Blank"
______________________CHAPTER1 ______________________
SYNOPSIS
SectiotJ Topics
1.1 Newtanian Mechanics
1.2 Wave Concepts and Electromagnetic Theory of Radiation
1.3 Inadequacy of Classical Mechanics
1.4 Planck's Quantum Theory
1.5 Photo Electric ~ffect
1.6 Weat Capacity of Solids
1.7 Atomic Spectra and Bohr's Hypothesis
1.8 Debroglie's Hypothesis
1.9 Compton Effect
1.10 Hiesenberg's Uncertainty Principle
3
4 Quantum Mechanics  A Comprehensive Text for Chemistry
d 2x
F=m ... (1.1)
x dt
(Newton's II law)
iii. "To every action there is an equal and opposite reaction." (Newton's III Law)
These laws of motion along with Newton's law of gravity provide a satisfactory explanation of
the motion of electrically neutral bodies of large dimensions (macroscopic objects) .
The basic concepts of the classical mechanics lies in the following points :
(1) The state of any object at any instant of time is completely determined by describing its
coordinates and velocities which are the function of time.
(2) If the state of the object and the force applied on it are known at some instant of time
using equation 1.1, state of the object can be predicted at any other time instant.
(3) Matter may be considered as made up of different particles, each of which can be studied
individually. •
(4) In the measuring process, it is assumed that the object of observation and measuring
instrument or observer are mutually independent from each other.
In brief  "motion of an object can be viewed as in sharply defined paths of motion of projectiles
or any other material body". This is the basic idea of classical mechanics.
At the end of the nineteenth century, Maxwell proposed that light travels in the medium in the
form of waves.
Light waves are transverse in nature. According to this theory, light waves are electromagnetic
in nature. That is why this theory is kown as Maxwell theory of electromagnetic radiation.
Electromagnetic radiation is being considered as being produced by the oscillating motion of electric
charge. This oscillation results in a periodically changing electric field surrounding the charge and
this also produces an oscillating magnetic field. These oscillating electric and magnetic field
disturbances propagate through medium as radiation. The range of wavelengths or frequencies of
these electromagnetic radiation is called as electromagnetic spectrum. This spectrum is given in
table 1.1.
Some characteristics of electromagnetic radiations are given below :
1. These radiations can propagate through space without the support of any medium and
travel in a medium with uniform velocity 2.99979 x 108 ms I •
2. These radiations are produced by the oscillations of electric charges and magnetic fields.
The electric and magnetic fields are at right angles to each other and to the direction of
propagation.
TABLE 1.1
Range of wavelength and frequency of electromagnetic radiation
Type of radiation Cosmic "frays Xrays UV Visible Infrared micro Radio
rays radiation wave frequency
Wavelength A (in m) 10 14_ IO B _ 10 10_ 108_ 107_ 10...{, 103_ 10 1_104
Frequency V (in Hz) 1022_ 1021 _ 10 18_ 10 16_ 10 15_ 10 14_ 10" 109_104
t
Energy
According to classical mechanics the following laws were given to explain the behaviour of a
black body:
Wein's Law: Wein established a relation between wavelength Acorresponding to the maximum
of the spectral distribution and the temperature of a black body. This law is known as Wein's
displacement lawand is given by :
. Amax T = Constt. ... (1.2)
Where constt. = 2.88 mmk
Constt
:::} Amax = .T ... (1.3)
1
or Amax o cT ... (1.4)
which implies that in the. spectral distribution of a black body its maximum wavelength i.e. Amax is
inversely related to the temperature of the black body.
Stefan  Boltzmann's Law: According to this law for a black body electromagnetic energy
per unit volume i.e. energy density can be related to the temperature of a black body as per the
following relation :
,
... (1.5)
Where E = energy density and ' J.,iis.a constant. This expression is also written in terms of
emittance R and is given by: '
... (1.6)
which is against the actual behaviour of a black body. Equation 1.7 was found to be satisfactory in
lower wavelength range but it fails to explain the experimental curves for a black body at higher
wavelength range.
(ii) Rayleigh  Jean Distribution Law: Rayleigh  Jean applied the principle of equipartition
of energy to black body radiation. This law considered a black body to be made up of a number of
oscillators with one possible frequency for each oscillator. According to it, an oscillator in equilibrium
with the source at a temperature T, possesses a mean kinetic energy kT where k is Boltzmann's
constant. The number of oscillators per unit volume (dN) in the frequency range v and v+dv is
calculated on the basis of classical view point as
87tv 2
dN= dv
c3
Where c is the velocity of light. Therefore, the energy density By dv is simply the product of the
number of oscillators per unit volume and the mean energy kT of the oscillator.
2
87tv kT dv ... (1.8)
Ev dv = c3
On increasing v, the energy density gradually increases without going through the maximum
and ultimately becomes infinite at v = 00. This situation leads to ultraviolet catastrophe. This theory
is also not in agreement with the experimental facts over the complete range of the wavelength.
The RayleighJean formula agrees fairly well with the experimental results in lower wavelength
region.
Neither, Wein Distribution Law nor RayleighJean distribution law are consistent with the
experimental results in the larger wavelength range. Therefore, this may be concluded that black
body radiation concept cannot be explain satisfactorily using classical mechanics.
En =nhv
Where n is any integer having value 0, 1,2,3, ................ .
Spectral distribution of a black body radiation can be explained on the basis of the theory of
Max Planck as following :
Let us consider that a black body consists of N simple harmonic oscillators, each having
fundamental frequency v. If these oscillators can take up energy only in the multiples of hv the
allowed energies will be 0, hv, 2hv, 3hv ............. Let No, N J, N 2, ........... be the number of
oscillators with corresponding energies Eo, E J, E2 .......... The number N j having energy E j above
the lowest energy level Eo can be determined using the Boltzmann's distribution law as:
N • = No exp (E/kT) ... (1.10)
N J = No exp (EJIkT) = No exp (hvIkT)
N2 = No exp (~IkT) = No exp (2hvIkT)
                  and so on
Where k is the Boltzmann's constant
The total number of oscillators (N) in all energy states is given by
N = No + N J + N2 + .........
= No + No exp (hvIkT) + No exp (2hvIkT) + .....
= No + [1+No exp (hvIkT) + No exp (2hvIkT) + ..... J
=No ~exp (.
~ 1hV)
 ... (1.11)
i=O kT
~.
= No hv ~ I exp
(.hV)
I kT ... (1.12)
00
No hv L i exp ( ihv/kT)
 E i=O
E= = ... (1.13)
N 00
No L exp ( ihvlkT)
i=O
00
hv L ixi
=> E= ;=0
~ . 2 3
LoiXI(1+X+X +X +.......... )
;=0
1
= (1 x)2 for x < 1
And numerator
00 •
= x (1 + 2x + 3x 2 + .... )
1
= (1 x)2 for x < 1
Therefore E will be
hvexp (IhvIkT)
=> E = ..:.''
lexp(hv)IkT)
hv
... (1.14)
E = (exp hv/kTl)
The number of oscillators per unit volume within the frequency range v & v + dv is given by
80v 2
dN= 3dv
C
Classical Mechanics and Origin of Quantum Mechanics 11
Therefore, energy density (E~ dv) in the region v & v + dv is simply the product of the number I
of•oscillators per unit volume and average energy of the oscillators. I
87tv2 hv
= Ey dv = CJ dv [exp'(hvIkT)1
87thv 3 1
= 3 ... (1.15)
C [exp(hvIkT) 1]
This equation is known as Planck's distribution equation. This equation can also be expressed
in terms of wavelength as
This equation was found to be in agreement with experimental results for a black body.
When hc » A kT (i.e. T or A is small)
exp (hc/AkT) » 1. So, one can be neglected in denominator.
hc
(Neglecting the·terms with higher powers)
=1 + AkT
= EAdA=
Or
.... (1.18)
or'
Example 1.1
Consider the Sun as a black body radiator. If maxima in the spectral distribution of Sun's
emitted energy appears at 480 nm. Calculate the temperature of the outer core of the sun.
Solution
According to Wein's law
A. max T = 2.88 mm K
2.88 x 1O3 mk
T = 480 X 109 m =600 k  Ans.
()
Fig. 1.3. Schematic Circuit diagram for the study of photoelectric effect
becomes zero. The limiting retarding potential, at which all electrons are stopped and at which
current becomes zero is called as stopping potential, 'V' for a particular metal surface and at a
given frequency.
v +V
t
j
w
'0
Vo v.
Fig. 1.5. Variation of kinetic energy with frequency of incident light.
14 Quantum Mechanics  A Comprehensive Text for Chemistry
It was shown by Einstein that this observation of the phenomenon of photoelectric effect
could be understood in terms of Planck's Quantum Theory. He pointed out that the emission or
absorption of energy takes place in quanta or photons of energy hv. When a photon of energy hv
(frequency vo), strikes with the metal surface it transfers its energy to the electron on the metal
surface., a portion of which is being utilised in emission of photoelectron and the rest of which has
been transferred to photoelectrons which is being utilised by this electron as its kinetic energy. So,
total energy of photon may be considered as the sum of work function and the kinetic energy of the
photoelectron.
hv =work function + kinetic energy
2
or hv = hvo + Yz mv ... (1.20)
where Vo is the threshold frequency or minimum frequency required to initiate the photoelectric
effect with its corresponding energy hvo and Yz mv 2 is the kinetic energy of the photoelectron
emitted with velocity v. The equation 1.20 is known as Einstein's equation for photoelectric
emission.
... (1.21)
E=3RT
C= (~~)V = [a(!~T)t
y =3R ... (1.23)
Where ow' is the oscillating frequency of the atomic oscillators in wave number units in the
lattice of the solid. From equation 0.24) one can predit that:
(i) At high temperature, the factor (hcro/kT)2 is small in comparison to unity. Hence C y =
3R. This is in agreement with the classical theory.
(ii) At very low temperature heat capacity approaches to zero. Therefore, at very low
temperature all the atoms in solids are in lowest vibration level, hence there would be
no vibrational contribution to the heat capacity.
(iii) On increasing temperature vibration energy increases, hence the heat capacity becomes
applicable.
Thus, Einstein equation explains the variation of heat capacities of solids with change in
temperature.
(iv) Spectral lines may appear in the atomic spectra of Hatom because of motion of
electrons from higher orbit to lower orbit and energy gap between the orbits involved in a
spectral transition i.e . .1.E is directly proportional to the frequency of that particular spectral
line
i.e. .1.E =En2  En 1 =hv ... (1.26)
On the basis of these postulates, Niel Bohr gave his theory to derive the formula for
electronic energy of an electron in a circular stationary orbit. This theory is valid for single electron
system such as Hatom, Be+ ion, Li 2+  ion, etc. The concept of Rutherford to explain the nuclear
model was in an explicit manner but one of the conclusions of this concept, that electrons revolve
round the nucleus in its own path, formed the foundation stone of Bohr's Theory. In order to
understand Bohr's Theory, let us consider the single electron system (Fig. 1.6).
,,
I \
\
\
, I
, I
, I
I I
I I
I I
I ,
I I
I
, ,
,,
\
\
\
, I
,
, , I
',....... ,,,"
........ ....... __ ......... , ... '
Fig. 1.6 Proposed Model for Hatom
According to postulate (ii)
Coloumbic force of Attraction between = Centripetal force of Moving of moving electron
Nucleus and electron
2
(Ze)e mv
Or (41tEo) r2 =r ... (1.27)
= ... (1.28)
Classical Mechanics and Origin of Quantum Mechanics 17
Ze 2
= ( ) = (mvr) v ... (1.29)
41tEo
nh
or mvr=
21t
... (1.30)
Or ... (1.31)
... 0.32)
For H  atom Z = 1 and if n =1 , the radius of the first Bohr orbit (ao) becomes
... (1.34)
1 1 Ze 2
=T (or K.E.) = (41t Eo) 2 r
... (1.35)
Ze 2
V (or P.E.) = 41t Eo r
Ze2 1 1 Ze2
Therefore E= +
n (41t Eo)r 2 (41t Eo) r
Ze2
E 
n  (41t Eo)2r
... (1.36)
For Hatom (Z = 1)
... (1.37)
(cons tan t)
En = ... (1.38)
n2
The above energy equation (1.36) is valid for certain discrete energy levels and n is the principal
quantum number here.
Origin of atomic spectral lines may be explained on the basis of energy equation derived by
Niel Bohr as per following :
According to equation (1.36) En (or energy) of electron in nth orbit is given by
21t2rne 4 z2
E ....,,,........,... ... (1.36)
n  (41tESn 2h 2
... (1.38)
... (1.41)
21t me z {1 1}
2 4 2
... (1.42)
= v = (41t eSCh 3 nt  nf
For Hatom (Z = 1 ) on substituting the values of constants in the above equation
Rydberg's formula
Where RH= Rydberg's constant for Hatom
And RH is equal to 109678 cm 1 or
1.09678 x 107 m 1
On the basis of the above equation (1.43) and according to Bohr's Theory, origin of atomic
spectral lines may be explained. As orbits are characterised by principal quantum numbers n
n=9
n=8
n=7
.~ r r
Humphery
n=6
r r r r n=5
Pfund
r ,r , n=4
~
Brackett
r " n=3
J, , , Pschen
n=2
~
Balmer
r n=1
Lyman
= 1, 2,' 3   , atomic spectral lines appear because of jumping of electrons from outer orbit to an
inner orbit as shown in Fig. 1.7. Following series of atomic spectral lines may be obtained in
atomic spectra of H  atom.
Luman series: n l = 1, n2 = 2,3,4,5 ...... ..
Balmer series: n l = 2, n2 = 3, 4, 5, 6 ...... ..
Paschen seri~s : n 1 = 3, n2 = 4,5,6, 7 ...... ..
Brackett series: n 1 = 4, n2 = 5,6, 7, 8 ...... ..
Pfund series: n 1 = 5, n 2 = 6, 7,8,9 ...... ..
Humphery series: n 1 = 6, n2 = 7,8,9, 10 ........
When energy is absorbed by an atom, the electron moves from ground state (n=l) to the higher
energy states (n > O. The amount of energy necessary to remove an electron from its lowest level
to infinite distance, resulting in the formation of a free ion is called the ionization energy (I). This
energy change for the Hatom is given by
Z 4
_21t e mz {1 1 }
... (1.44)
.1E = (41t Eo)ZhZ nf  nt
_21t Ze4 m21
2 ... (1.44)
(41tEo)2h 12
Example 1.2: A beam of electron is used to bombard gaseous hydrogen atoms. What is the
minimum energy the electron must have if the number of Balmer series, corresponding to a transition
from n = 3 to n = 2 state is to be emitted?
as
m = 9.1 x 031 kg ; e = 1.602 x 1019 C ;
1t = 3.1415; 41tEo = 1.113 1010, C 2 r l m I and h = 6.626 X 1034 Js and n 1 = 2 and n 2 = 3 on
X
substituting tqe values of all the constants and n 1 & n2
E = 2.98 X 1019 J
Example 1.3 : Calculate the third ionization energy of Lithinm
2
The third ionization energy of lithium means the removal of an electron from Li +
Since Z = 3 we have
Classical Mechanics and Origin of Quantum Mechanics 21
=6E
2n2e4 rn
= 6E = (4n Eo)2h2 (3)2
On substituting values ofn = 3.14)5; m = 9.1 x 1031 kg;e = 1.6 x 1019 C; h= 6.626 X 1034 Js
and 4nEo = 1.113 x 1010 C2N"1 m2
1= 16EI = 1.962 x 10 17 J for lithium
Sho·rtcomlngs of Bohr's Theory :
Though Bohr's Theory had explained well the origin of atomic spectral lines and explained the
spectral data for Hatom: But it did not give the explanation for their fine structures as observed
with spectroscopes of high resolution power or about splitting of spectral lines in presence of
external magnetic or electric field.lt had also not accounted for the spectra of other atoms or molecules
and intensity variations in spectral lines. Arbitary stationary orbits have given us theoretical basis
and the stability of the orbits can't be understood easily, on the basis of Bohr's theory. Pictorial
concept of electrons in orbit is not justified.
Another major shortcoming of the .Bohr's theory is its proposal for angular momentum of
electrons. According to this theory, angular momentum for moving electron is the integral multiple
ofh (or hl2n) which is not true, as in certain cases electrons also possess the zero angular momentum.
h h
A=orA= ... (1.48)
me p
Where p is momentum of photon and c is the velocity of light, with m is mass of photon.
Therefore, the wavelength of moving photon which exhibits wave like behaviour is also inversely
related to its momentum. Later on, this observation was extended to micro particles like electron
also, and c (velocity of photon) was replaced by v (velocity of electron).
h
A= ... (l.4~)
mv
h
Or A=  .. , (1.49)
Pe
Where Pe = momentum of electron and is equal to mv and m is mass of electron.
Experimentally Debroglie's wavelength A. can be determined as follows: When an electron
is accelerated through a potential difference of V volts, its kinetic energy will be
1
mv 2 =Ve ... (1.50)
2
mv = (2meV)1 ... (1.51)
Where m, e and v are the mass, charge and velocity of the electron respectively.
Therefore
h
A= mv
h
Or A= (2meV)i ... (1.52)
h
It is obvious  is negligible for relatively large objects (macroparticles), while for subatomic
mv
particles (microparticles), this quantity is not small enough to be considered as negligible. Therefore,
one may conclude that wave character is predominant in micro particles and particle character is
predominant in macroparticles.
The Debroglie concept does not imply that matter behaves like a particle at one time and like
waves at other time. Rather the wave nature has to be an inherent propecty of each particle. Micro
particles are capable of exhibiting particle or wave like properties to some extent, depending upon
Classical Mechanics and Origin of Quantum Mechanics 23
A=~
mv
h =6.626 X 1034 Js; m = lkg and v =10m/sec. On substituting these values.
A= 6.626 X 1034 cm or 6.626 x 1029 m
Example 1.5 : An electron is accelerated by applying a potential difference of looOV. What is
the DeBroglie wavelength associated with it?
h
As A = (2meV)!
lev = 1.6.2 x 10 19 J
34
A= 6.026 X 10 Js
(2 x 9.101 x 10 kg x 1.602 x 1019 J x 1000V)~
31
= A = 38.7 X 1012 m
Incident
Xrays
Since the scattered xrays have larger wavelength than the incident, it is evident that scattered
. 1
radiations shall have lower frequency (v OC i) and hence, they are of lower energy. Now since
scattering is produced by the loosely bound electrons on the surface of the elements it appears that
some interaction between the xrays and electrons has taken place as a result of which wavelength
of xrays increases or energy of scattered xrays decreases. If these scattered radiations are examined
with the help of xray spectrometer, two sets of spectral lines are obtained, one of the original xray
frequency and other of the lower frequency than that of the incident frequency. These lines are
called Compton lines. Compton Effect can be shown as fig 1.8.
Assuming the xrays to consist of particles each having energy hv and momentum hv/c. Compton
calculated the increase AA in the wavelength by ordinary considerations of conservation of energy
and of momentum with the help of the expression ,
h ~
AA = me Sin2 2
h
AA = A~  A =  (1  cos 8)
me
Where A' is the wavelength of the scattered photon which is larger than that of the incident
wavelength Am is the mass of electron and 8 is the angle between the incident and scattered xrays.
AA is called shift in wavelength or Compton shift.
Dependence of Compton shift on the scattering angle e :This is understood by the following
three cases :
Case I 8 (or angle of scattering) is 0°
Therefore Cos 8 =Cos 0 = 1 or Sin2 8/2 = 0
2h
=AA=  xO=O
me
Hence, scattered wavelength will not change
Case II 8 «or angle of scattering) is 90°
In this case Sin 812 = Sin2 (45°)
2
2h 1 h
AA=  x  = 
me 2 me
2h
= A').. =  x 1 = 0.0484 A 0
me
Or Ax . Av ~ 1iI41tm
For numerical purposes product of Ax and A.p may be taken as equal to 1112, where Ax is
uncertainty in position and Ap is uncertainty in momentum. One another statement of the uncertainty
principle can be expressed in terms of uncertainty in energy (AE) and uncertainty in relaxation time
(At) as
AE . At ~ 1iI2
or AE . t ~1iI41t
or h Av . At ~1iI41t
or Av . At ~ 1I41t
This statement of the uncertainty principle has its use in spectroscopy as band width for any
spectral transition can be explained on the basis of this statement of uncertainty principle.
Example 1.6 : Calculate the product of uncertaiqty in position and uncertainty in velocity for
an electron wh~se mass is 9.1 x 1031 kg.
As Ax . Ap ~ (or 4~)
Or X
 !.
. mAv > 2 (or 4n ~)
26 Quantum Mechanics  A Comprehensive Text for Chemistry
h
Or Ax. Av 3
41tm
Since m = 9.1 x 1031 kg h = 6.626 X 1034 Js & 1t = 3.1415
6.626' 10'34
=Ax. Av:;: 4' 3.1515' 9.1 • 1O31 kg
=5.78 x 105 m2 SI
Fund3;mental Concepts of
Quantum Mechanics
SYNOPSIS
Section Topics
2.1 Introduction to Sinosidal equation
2.2 Schrodinger's Wave Equation
2.3 Postulates of Quantum Mechanics •
2.4 Introduction to wave function
2.5 Operator's Concept
2.6 Concept of Eigen Value and Eigen Function
2.7 =
To show H '¥ E'¥ is operator form of Schrodinger equation
2.8 How to write Hamiltonian operators for different atomic or molecular systems
Chapter  I of the present book deals with the fundamental concepts pertaining to the origin of
quantum mechanics. This mechanics may be treated as mechanics of limited scope as only Hatom
problem can be solved with the help of it accurately even then this may be treated as mechanics of
wide scope as all other huge molecular systems can be solved on the approximation using quantum
mechanics. In this chapter, fundamental concepts of Quantum Mechanics are dealt with. This chapter
includes introduction to sinosidal equation, derivation of Schrodinger equation, save function and
its physical significance, operator's concept, postulates of quantum mechanics etc.
27
28 Quantum Mechanics  A Comprehensive Text for Chemistry
Matter waves can be expressed on the basis of an equation called sinosidal equation for wave.
Sinosidal equation may be expressed as follows:
y = A Sin (27t vt) ... (2.1)
Here y is the displacement during propagation of wave, A is amplitude of the wave, v is the
vibration frequency and t is time. This equation can also be expressed as
y = A sin (27t t)
y = A sin (rot) ... (2.2)
Where ro is angular velocity and v == ro/27t or ro = 27t v
27tVX)
y =Asin ( c ... (2.3)
21CX
Therefore Y Asin
 A ... (2.4)
2ltx
'I'  A sin A. ... (2.5)
''P' the wave function Mre is the function of space and time and may be expressed as
'I' = f (space, time) or f (x,t) ... (2.7)
Or 'I' = 'I' (x) f(t)
a 'P
2 1 a 'P(x)cos(21tivt)
2
ax 2 = C2 at 2
Fundamental Concepts of Quantum Mechanics 29
... (2.9)
Equation 2.6 is a time dependent equation and equation 2.9 is an time independent equation
a ,¥(x)
2
4n 2 v 2
ax 2 = cz '¥ (x) ... (2.9)
c =VA
Or
... (2.10)
h h
A=or
mv p
I P
 =
A h
1 p2
Or ... (2.11)
A,2 = 11
Substituting the value of 1n..2 in equation 2.10
Or
... (2.12)
As energy of electron may be considered as sum of its kinetic energy and potential energy
E=T+V
T (or K.E.)=E  V ... (2.13)
Since T (or KE) = Y2 mv 2 ... (2.14)
30 Quantum Mechanics  A Comprehensive Text for Chemistry
Multiply numerator and denominator of equation 2.14 by om' mass of electron (or micro
particle)
T = m 2 v 2/2m
Or m2y2 =2m T ... (2.15)
Substitute the value ofT from equation 2.13 in equation 2.15.
m 2 v 2 = 2m (EV) ... (2.l6)
Substituting the value of m 2 v 2 from equation 2.16 in equation 2.12
a 'P(x)
2
 41t2m(E  V)'P (x)
=
This is time independent Schrodinger equation for a single particle of mass Om' moving in one
direction only. Considering the motion of microparticle in three dimension, this equation has been
modified as
Or ... (2.18)
Equation 2.18 is threedimensional time independent Schrodinger wave equation for micro
particle which serves as the basis for quantum mechanics. Here in this equation'll is the function of
three dimension space.
i.e. 'II = f (x, y, z)
or 'II = 'II (x) 'I' (y) 'I' (z) ... (2.19)
Table 2.1
Quantum Mechanical equivalents for physical quantities
Physical Quantity Quantum Mechanical (equivalent) operator
Space x x
y y
z z
Momentum Px = mv x
h a (x component)
21ti ax
h a (y component)
21ti ay
h a (z component)
21ti az
Kinetic Energy
I
T=  mv 2
2
2m
Potential Energy V
Total Energy E
Postulate III :The possible values of any physical quantity of a system (eg. energy, momentum,
etc.) are given by the Eigen values 'a' in the operator form of equation
... (2.21)
Where Ais the operator corresponding to the physical quantity and'll is the Eigen function. In
other words, each single measurement of a physical quantity, A(A operator) given an Eigen value 'a'.
32 Quantum Mechanics  A Comprehensive Text for Chemistry
Postulate IV :The expected, average (or expectation) value of a physical quantity <.A> of a
system, whose state function is 'P is given by
J'P'I A1'Pd't
<A> = J'P'I'Pd't .:'. (2.22)
< ",'IAI",*>
or <A> =
< ",I",' >
If '¥ is normalized
Postulate V :The wave function that represents the state of the system changes with time,
according to the time dependent Schrodinger equation
J'P
in Tt(X,y,z,t) ~ 'P ( x.y,z,t )
=H ... (2.23)
r17~~X
Here qt* is a complex conjugate of qt, probability from P.I. expressed in equation 2.31 or 2.32
will also come out to be real as qtqt* will be real, as shown below
If qt = a + ib (say)
34 Quantum Mechanics  A Comprehensive Text for Chemistry
Then
'1'* = a  ib (its complex conjugate) ... (2.33)
So, 'I' '1'* = (a + ib) (a  ib)
= a2 _ (ib)2
= a2  i2 b 2 (F = 1)
'I' '1'* = a2 + b2 (real) ... (2.34)
Therefore, this may be concluded that instead of '1', '1'2 rather 'I' '1'* has its physical significance.
Normalized and Orthogonal wave function :
As it has been shown above in the same section that '1'2 (or 'I' '1'*) are physically significant
and are in use to evaluate probability from probability integrals as expressed in equations 2.25,
2.26 2.31 and 2.32.
According to the rule of mathematics probability may have value zero (minimum) to one
(maximum).
If value of probability is one
f 'I'2d't = 1 or f 'l"Yd't= 1
over whole
over whole
space space
+00 +
In this case function will be normalized function and the condition expressed in equation 2.35
is normalization condition.
If value of probability is zero.
+00 +00
Or f '1'2 d't = 0 or f '1"1'* d't = 0 ... (2.36)
This is the condition of orthogonality and function 'I' is orthogonal to '1'* (i.e~ its complex
conjugate)
If wave function '\}1' is a normalized wave function and it follows the condition as expressed in
equation 2.35, normalization constant may be determined as follows:
+~
=>
Or ... (2.38)
Or ... (2.39)
In equation 2.39 (.Jk.) 'I' is normalized wave function with (.Jk )'1'* as its conjugate part
and (.Jk ) is normalization constant.
(a)
(b)
x+
(c)
Fig. 2.2 (a) An acceptable function as it is single valued, finite and continuous function.
36 Quantum Mechanics  A Comprehensive Text for Chemistry
:7tl2
I
I
,I
Fig. 2.3 Sin x (within 0 ~ x ~ rc/2)
(ii) cos x will also be an acceptable wave function in the specified range 0 ~ x ~ nl2
(iii) tan x will not be acceptable wave function at all as it tends to infinity at x =rt/2 as it is
clear from its graph
f~'d't=N
As over whole (equation 2.37)
space
N = 3 (given)
=> ~ f~'d't=l
Or kf~'d't=l
Fundamental Concepts of Quantum Mechanics 37
1 1
which implies that .IN =.Jj will be
1
The normalization constant and normalized wave function will be .Jj '1'.
TABLE 2.2
Some examples of operators used in mathematics
Operator Operation
d
dx
(~or~)
dy dz
To differentiate the function w.r.t. x (or y or z)
Like mathematics, operators have their significance in quantum mechanics also as operators
may be used to find out physical quantity (or observable) in quantum mechanics. For every observable
(or physical quantity) there exists a quantum mechanical equivalent operator as shown in table 2.1.
An operator in quantum mechanics is designated by the (1\) cap. Symbol or by subscript op as
Properties of operators
Although operators do not have their physical meaning, they can be added, subtracted or
multiplied and have some other properties also.
Addition of operators
~, a 2 ,
2
The addition yields new operator e.g. \72 is addition of three differential operators viz.
ax 2 ay
38 Quantum Mechanics  A Comprehensive Text for Chemistry
As
... (2.41)
Subtraction of operation
Like addition, subtraction of operators can also be done and it would also yield a new operator
.. .. d
e.g. A ; loge B =  & '¥ = x2
dx
or (
log
e
_~)X2
dx
=>
A B'¥ = A[B'¥]
As B'¥ = <I> (say)
.
A [B'¥] = A<I>
If A<I> = x (say)
= A.B'¥= A[B'¥]=A<I>=X ... (2.44)
... (2.45)
For any two operators A & B, the difference A B B A, which is denoted by [A. B] is called
commutator operator. If [A, B] = 0 it is called as zero operator.
Fundamental Concepts of Quantum Mechanics 39
Linear Operator
An operator A is said to be linear if its application on the sum of two functions gives the result
which is equal to the sum of operations on two functions independently i.e. if it follows. The
following conditions
Hermitian Operator
An operator will be hermitian operator if it follows the following condition
f'¥IAI'¥*d't f'¥*IAI'¥d't
over whole = (lvcr whole ... (2.47)
space space
d
Example 2.S Show that Px =  iii dx is Hermitian operator. To show this, let us consider f is
ff"pJdx = ff pJ* dx
L.H.S. of the above equation is = ililffl:oo
a2 a2 a2
V2 = ax2 + ay2 + az2 ... (2.48)
40 Quantum Mechanics  A Comprehensive Text for Chemistry
... (2.49)
Equation 2.49 is operator's form of Schrodinger equation, it is shown later in Section 2.7.
2.6 Concept of Eigen value and Eigen function
If a function follows the following equation
It is said to be an Eigen function and equation 2.50 is an Eigen equation. In this equation, A is
AOperator which is operated on '¥ to yield a constant value 'a', the Eigen value (or possible value
for any physical quantity).
Example 2.6: Show that '¥ = Sin 2x is an Eigen function for the operator ()2/ax2
a 2/ax2 (operator) is operated on wave function '¥ =sin 2x as per follows
This shows that '¥ =sin 2x is a Eigen function for the operator a 2/ax2 with Eigen value 4.
I
T = mu
2
J
... (2.52)
Where Px' Py & pz are components oflinear momenta along x, Y, & z directions and taking their
quantum mechanical equivalents (table 2.1)
Fundamental Concepts of Quantum Mechanics 41
... (2.56)
Or ... (2.57)
as since F =1
_h
2
[ a az aZl
2
... (2.59)
Or ... (2.60)
Or
Or ... (2.63)
Or ... (2.64)
Or
42 Quantum Mechanics  A Comprehensive Text for Chemistry
Which is the required Schrodinger wave equation. This proves that 11'1' = E'P is operator fonn
of Schrodinger wave equation as this equation, can also be derived from H'P = E 'P equation.
". (2.66)
... (2.67)
Fundamental Concepts of Quantum Mechanics 43
... (2.68)
... (2.69)
18. If f'P'P*d't =2, find out normalization constant for 'P. (See section 2.4) [Ans. Y..fi]
19. Prove that 1.JI =cos 2x is an Eigen function for the operator iJ2/CJx 2 . Find out its Eigen value (See section
2.6) [Ans. 4]
SECTION2
3. Quantization of Transation Energy
4. Quantization of Vibration Energy
5. Quantization of Rotation Energy
6. Hydrogen like Atoms
"This page is Intentionally Left Blank"
_____________________ CHAPTER3,_____________________
SYNOPSIS
Section Topics
3.1 Particle in a one dimensional box
3.2 Free electron model (An application of particle in a box problem)
3.3 Particle in three dimensional box
3.4 Particle in a cubic box
3.5 Particle in a Circular Ring
3.6 Tunnelling
In this chapter, concepts related to quantization of Translational energy are being discussed.
Translational energy is least among all modes of energies attained by any particle viz. vibration,
rotation and electronic energies etc. Quantization of Translational energy can be studied in terms of
particles considering them in boxes of different dimensions.
x=o x~ x=l
Fig. 3.1 Consideration of a particle in a onedimensional box.
48 Quantum Mechanics  A Comprehensive Text for Chemistry
Let I be the length of the box. Above consideration (Le. Vex) (at x = 0 & x = l) = 00) shows that
the particle is deeply buried inside the box.
Schrodinger wave equation for the particle outside the box will be
a ,¥(x)
2
2 +
8n 2 m
2 (E  00) '¥(x) =0 ... (3.1)
.ax h
Or ... (3.1)
Solution of above equation shows that the particle does not exist outside the box as out side the
box'll (x) = o. Therefore, this may be concluded that the particle is deeply buried inside the box.
Schrodinger equation for the particle inside the box may be written as
... (3.2)
Or
a ,¥(x)
2
8n 2 m
+  2 E'¥=O ... (3.2)
ax 2 h
To solve this equation, let us suppose
2
8n mE _ A}
h2 
... (3.3)
a ,¥(x)
2
... (3.13)
... (3.14)
Above equation 3.14 shows that the translational energy E is quantized and depends lipon the
quantum number (n 2)
Applying nonnalization condition to 'I' (x) as 'I' (x) should be normalized in itself.
x=/
X =IA2 • 2 (n1tx)d 1
~
Jn.SlD
x=o

1
X=
Or
A2=~~A=
I ' VIII .,. (3.16)
To show the orthogonality of wave functions, let us apply the condition of orthogonality to
wave functions
J'1':'I' d
ovcrwbole
m '!: =0 ... (3.18)
space
Where m & n are different quantum numbers. For a particle in onedimensional box
~
m1tx)
'1'*m ='I'm
=  sin '
i( l '" (3.19)
~
n1tx
and 'I' =  sin '" (3.20)
nil
50 Quantum Mechanics  A Comprehensive Text for Chemistry
.=1
J'1':'1'nd't =0
.=0
2 'J=I sm
. (m1tx)
  sm. (mtx)
  dx ... (3.21)
I ,=0 I I
Or which is equal to
! [(
I
I ) sin {(m  n) 1tlx}  ( 1) sin {(m + n) 1tX
m+n1t m+n1t I
}]I . .
0
(3.22)
Since m & n both are integers the above expressions is numerically equal to zero which shows
that the different wave function that are generated from equation 3.17 for particle in a box problem
will form orthogonal set of wave functions. As 'I' (x)'s are normalized in itself and orthogonal to
each other, therefore, this can be concluded that 'I' (x)'s for particle in a box problem are orthonormal
set of wave functions.
From equation 3.14 different energy levels may be obtained as
Viz.
(or 9 E 1) and so on. Graphs of 'I' (x) and 'I'2(X) can be plotted as shown in figure 3.2
A few features of a particle in a box problem:
Un case of particle in a box problem wave function 'I'(x) is zero at walls, the length' l' of the
box must be an integral multiple of half wave lengths i.e.
I =n ().J2) ... (3.23)
This can be shown as follows
Quantization of Translation Energy 51
16E,
16E,
(n=4)
9E,
9E,
n=3
4E,
4E,
n=2
E, E,
n=1 I
~I 1jI(x)
Fig. 3.2. The energies, wave function 'I'(x) and probability densities 'l'2(X) of a particle in a box.
E =n 2
••• (3.14)
And E = ~ mv (=K.E.)
2 ... (3.24)
Or E = p2/2m ... (3.25)
Using de broglie's equation
E = (~r
2m
=~
2mA.2
... (3.26)
Equating energy of the particle inside the box by equation 3.14 and equation 3.26.
n 2h2 h2
=8m/2 = 2mA. 2
=>
52 Quantum Mechanics  A Comprehensive Text for Chemistry
Therefore, function besides having zero value at boundaries, it also' has zero value at some
points within the box, as shown in fig. 3.2. These points where 'I'(x) = 0 (or rather the points where
'¥(x) is zero) are known as nodes and can be expressed by the formula
No. of nodes = (nl) ... (3.28)
2. The energy associated with wave function increases with increase in number of nodes of
the wave function 'I'(x)
3. Wave functions may be categorised into two categories w.r.t. their symmetry
Symmetric wave functions (or even wave function)
'¥ (x) = '¥ (x)
And anti symmetric wave functions (or odd wave functions)
'I' (x) =  'I' ( x)
From fig. 3.2 it is clear that '1'" '1'3' '1'5   are symmetric and '1'2' '1'4' '1'6   are
anti symmetric wave functions w.r.t. centre of the box.
4. The probability densities is not uniform at all the points in the box for particle while it
varies with nand 'I'(x).
Or
h2
Or AE = [(n+l)2 n J 8m/2
2
h2
Or AE = (2n+ 1) 8mf ... (3.29)
Example 3.1: Evaluate expectation value < x > and < p > for a particle in onedimensional box
of length I.
Quantization of Translation Energy 53
2 0 Icos (  
2nxx)] 2
=T[x [ 2 1 dX=(7)(~)=~
I
=j\f'(x)
o
I h. d 1'I'X dx
2m dx
\
__  s. m
h I' (2)
 2xi 0 1
 ds m
(nxx)\
1 dx
 dx
(nxx)
I
I'
= 2xi I!
h (nx) I (2)
T sm. (nxx)
[ cos (nxx
1 ) dx = 0
Example 3.2 : Evaluate the expectation value of Kinetic energy of a particle in a onedimensional
box.
As the kinetic energy of the particle is given by
T=.!mu
222m
=.!L 2
1 m2t}2
or T=i;
t l(ha)2
= 2m 2xi ax = 8x 2m ax 2
J'
=m(8~~~Hsin(n7) !',ISin(n;x}x
=m(8~~:) ((n;J) [Sin'(n7)dx
=m(8~~:) (n;)' H[1cos(2n;x)dx
(6.626 x to 34 )Js
~ = (2 x 2 + 1) 8(5.78 x 10lO m)2(9.11 XI03I kg)
= 9.02 x 10. 19 J (or 4.54 x to4 cm· l )
z
Fig. 3.3 : A particle in three dimensional box of dimensions a, b & c :respectively.
Schrodinger equation for this particle may be written as
... (3.30)
2
a a2 a2
Here +  2 = V2 is Laplacian operator
ax 2 ay2 az
Wave function for this particle will be
'I' = f (x, y, ~) = 'I'(x) 'I'(y)'I'(z) ... (3.31)
And Energy E for this particle will be
E = (Ex + Ey + E z) ... (3.32)
Equation 3.30 can be resolved into three simpler equations (as similar to the particle in a one
dimensional box problem) as
... (3.33)
... (3.34)
And
a 2
81t 2m
az 2 'I'(z) + ~ Ez 'I'(z) = 0 ... (3.35)
Similar to onedimensional box problem, solutions for the equations 3.33, 3.34 and 3.35 are
56 Quantum Mechanics  A Comprehensive Text for Chemistry
{2 (ny1tz)
'¥(z) + ~a sin a ... (3.36)
[2 (n y1ty )
'¥(y) + ~b sin b ... (3.37)
... (3.38)
~ . (nx1tx) . (n y y . (nz7tz)
'¥  sm   sm 1t) sm  ... (3.42)
 abc abc
It is apparent from this equation that in a cubic box energy depends upon the sum of squares of
quantum numbers nx ,~ and nz if sides of the cube are equal. In this case, energy levels of different
st::ts of quantum numbers may have same energy which leads to degeneracy of levels and the number
of different states belonging to the same energy level is known as degree of degeneracy. Table 3.1
shows energy levels corresponding to different states with their degree of degeneracy .
Quantization of Translation Energy ·57
TABLE 3.1
Energy levels and degeneracy of various states
Quantum Numbers(n" n, n) and States Energy Degree of Degeneracy
(1, 1, 1) 3h2 /8m a2 Non  degenerate
(211) (121) (112) 2 2
6h /8ma Three  fold degenerate
(221) (212) (122) 2 2
9h /8ma Three  fold degenerate
(311) (131) (113) 2 2
11h /8 ma Three  fold degenerate
(222) 2 2
12 h /8 ma Non  degenerate
(123) (132) (213) 2 2
14 h /8ma Six  fold degenerate
(322) (232) (223) 2 2
17 h /8a Threefold degenerate
Example 3.4 : Find the lowest energy of an electron in a threedimensional box of dimensions
0.1 x 10 15 , 1.5 X 10 15 and 2.0 x 10 15 m.
Total kinetic energy for a particle in threedimensional box is given by
6.626 x 10 Js )
E = ( S x 9.1 X 1031 kg
34 []2
(0.1 x 1O ls i
12 e]
+ (1.5 x 1Ols )2 + (2.0 X 1Ols )2
=6.06 X 10 8
J
Example 3.5 : Determine the degeneracy of energy level 12h2 / Sma2 in a cubic box.
Energy of a particle moving in a cubic box is given by
2
h
E = Sma 2 nx +ny +n z
[2 2 2J
a = b = c for cubic box
Given energy E = 12h2/Sma2
Therefore,
n x2 + ny2 + nz2 = 12
58 Quantum Mechanics  A Comprehensive Text for Chemistry
... (3.45)
... (3.47)
... (3.47)
Quantization of Translation Energy 59
Will be
'II =A sinA. x + B cos A. x ... (3.50)
The boundary conditions are different from those of a particle in onedimensional box. According
to equation 3.46
'11(0) = 'II (c) ... (3.51)
Therefore,
B =A sin A.X + B cos A. c ... (3.52)
In this case, 'II and its differential a'lllax must be continuous. Therefore,
... (3.53)
Which leads to
AA. = AA. Cos A. C  B A. Sin A. C ... (3.54)
Multiplying equation 3.52 by B A. and equation 3.54 by A and then adding them
Cos A. C = 1 ... (3.55)
Or J. C= 2n1t = A. = 2n1t
C
... (3.56)
Where n =O. ± I, ± 2, ± 3 ............ The energy levels for such a particle are given by
... (3.57)
This result may be compared with a particle in a box. It differs in two aspects. In this case n can
have values of zero, positive and negative integers so that each energy level is doubly degenerate
(except n =0). For state having n =0 (E =0) the wave function j.,
'II0 =B =constant
Which shows that there is no variation of'll round the ring in the lowest state
The normalization of'll gives
=> J. (2n1t)
C
N 0 sm C xdx + Jcos (2n1t)
C x dx +
C
B2 0
2
. JC'sm (2n1t)
2AB 0 C xcos (2n1t)
C xdx=1 ... (3.59)
60 Quantum Mechanics  A Comprehensive Text for Chemistry
'¥
{2 cos ex sin
= V~ (2n1t)
c +
(2
V~ sin ex cosm
(2n1t)
c x ... (3.63)
3.6 TUNNELLING
Let us consider a particle in a onedimensional box of length I with walls of finite height &
width which shows that potential energy have finite values at the walls and upto a certain distance
from walls (Fig. 3.5). The potential energy is thus defined as
V = 0 for x < 0 and x > 1
V = Vo for 0 S; x S; 1 ... (3.64)
Let in region II, the total energy E is less than that of the potential energy barrier Vo of finite
width (say b). According to classical mechanics, this behaviour of a particle is not allowed because
its kinetic energy (K.E.) is always greater than or equal to zero. Hence, total energy E = K.E. +Vo
implies that kinetic energy must be a negative quantity if E is to be less than Vo' This behaviour of
the particle can be justified in quantum mechanics.
Region II
Region III
Region I
"
o~o~rx
(a)
(b)
(b) The wave function of particle shows its existence even outside the box.
d 2,¥ 8x 2m
2 + h 2 (E  V 0) 'II = 0 ... (3.67)
dx
The general solution of this equation in Exponential form is given by
'I'(x) =Aexp [( 2~X }J(E _V,)2m ] + B exp [( 2:iX )~(E  V,)2m ] ... (3.68)
... (3.71)
62 Quantum Mechanics  A Comprehensive Text for Chemistry
This solution describes the behaviour of wave function within the potential energy barrier. The
probability of finding particle within this region is a positive quantity. With increase in distance (~)
in region II along the positive direction of the barrier the probability '1'2 decreases exponentially. If
barrier is not infinitely high (V 0* 00) and not with infinite width (b '* 00) there will be certain
probability that the particle exists in region I & III also. In other words, particle can penetrate
through the barriers. Such a penetration or leakage of particle is known as tunnelling or quantum
mechanical tunnelling. This phenomenon is important for particles of low mass like electron, proton,
etc, The emission of a.  particles from radioactive nucleus is a process of tunnelling. In C 2H 6
molecule, Hydrogen can undergo tunnelling through the barriers from one staggered position to
another. Tunnelling of electron is also important in the redox reactions.
1. Derive wave function for particle in a one dimensional box. (See section 3.1).
2. Explain the concept of quantization of translational energy (See section 3.1)
3. Derive an expression for energy of a particle in threedimensional box. (See section 3.3)
4. Show normalization of wave function of a particle in one dimensional box (See section 3.1)
5. Derive energy expression for a particle in a box considering it as free electron model (See section 3.2).
6. Explain the degeneracy of energy levels taking example of particle in a cubic box (See section 3.4).
7. Derive expression for energy of a particle moving in a circular ring (See section 3.5).
8. "Phenomenon of penetration of a particle through barriers is known as tunnelling." Justify this statement
with derivation. (See section 3.6).
9. Show that the length of the box is an integral multiple of iJ2 where A. is the wavelength associated with
the particle wave (See section 3.1).
10. Consider electron in a box of size of the nucleus (10 14 m). Calculate its. ground state energy.
(Ans. 6.03 x 10010J).
2
11. Determine the degree of degeneracy of the energy level 17h /8mP of a particle moving in a cubic box.
12. What are the degrees of degeneracies of the first three energy levels for a particle in a three dimensional
box with a =b =2c?
13. Consider an electron in a one dimensional box of length 20Ao • What is its energy in ground state?
[Hint: taking n = 1, EI =h2/ 8 mP, I =20 X 1010 m; substituting value of hand m. = 9,1 x 1031 kg; EI
can be calculated] (Ans. 3.01 x 1019 J).
____________________ ~CHAPTER_4 _____________________
SYNOPSIS
Section Topics
4.1 Classical treatment for harmonic oscillator
4.2 Quantum mecha.nical treatment for hanoonic oscillator
Apart from translation mode, a particle can have vibration mode also. In order to understand
the vibration modes and quantization of vibration energy, a particle may be considered as a simple
harmonic oscillator. In this chapter, concepts related to oscillations are discussed.
In harmonic motion the restoring force 'F' acting on the particle, is proportional to the amount
of displacement 'x' from the equilibrium position
Foc:x ... (4.1)
Or F=kx ... (4.2)
Where k is the force constant and is a measure of stiffness of a spring if we consider a spring as
harmonic oscillator. A strong and inflexible spring will have larger value of k while' a weaker
spring will have lesser value ofk. Negative sign in equation 4.2 indicates that the restoring force is
always in the opposite direction to that of displacement in the oscillator. A simple harmonic oscillation
in a spring can be shown as in fig. 4.1
d2x k
  x
 dt 2  m
... (4.5)
This shows that the frequency of vibration of an oscillator (i.e. v) depends upon the restoring
force constant k and mass of the particle m.
The potential energy of the particle at any instant is evaluated as per follows :
Since F =  dV/dx ... (4.10)
i.e. force can be expressed as differential of potential energy w.r.t. displacement x. Substituting
value of F from equation 4.2
dV =kx dx ... (4.11)
on integrating this equation
kx 2
V=+I ... (4.12)
2
Here I is the integration constant whose value can be evaluated on substitpting the limits i.e. at
x = 0; V = O. This gives I = 0, therefore, expression for the potential energy becomes
kx 2
V=T ... (4.13)
Quantization of Vibration Energy 65
The variation of potential energy with displacement x is shown in the figure 4.2. The momentum
of the particle at any instant is given by
p =mv ... (4.14)
dx
or p=m ... (4.15)
dt
Considering x = A sin (21tvt) ; momentum p of the particle, showing harmonic oscillation, is
given by
p = m A «21tv) Cos (21tV't) ... (4.16)
Fig. 4.2 : The parabolic variation of potential energy of the harmonic oscillator
Total energy of this particle at any instant is the sum of its kinetic and potential energy.
E=T+V ... (a.17)
Or E =Y2mv 2 + V ... (.1.1R)
Or
E = m A
2 2
(Ym) cos (2nvt)
2
+ kA 2 sin2(2nvO
... (4.22)
2m 2
66 Quantum Mechanics  A Comprehensive Text for Chemistry
pZ
T=
2m
_h 2 a z
Or 'F = 81t 2m ax 2 ... (4.24)
1
V =  kx 2
2
Quantization of Vibration Energy 67
H=t + V
_h2 a2 ", 1
 +kx.2 ... (4.25)
 81t 2 m ax2
2
Therefore, Schrodinger equation for the system may be written as
It is found that the well behaved solutions exist for the equation 4.26 only for the following
Eigen values E
Or E =(V+Y2) 
y
h~
21t

m
... (4.27)
Where v is the vibrational quantum number which can have values v = 0, 1, 2, 3, ....... Equation
4:27 may be rewritten as
Ey = (v + Yl) hw ... (4.28',
The wellbehaved solution for the Schrodinger equation 4.26 for the first few lvwest states
are given by
These wave functions are given using Hermite polynomials Hv (y) where y = ax. Figure 4.3
,hows the plots of first few levels of harmonic oscillator wifh their relative energies. These are qt
md qt2 (probability densities) graph.
68 Quantum Mechanics  A Comprehensive Text for Chemistry
Y\f\M~.
I
I
I
9/2 hu
7/2 hu
1\[\[\[(
I
I
I
I
I I
)(LN
5/2 hu
V : I
1\/l
I
I I
I I
I
3/2 hu I I
I I , I
I I
I
,
'. I
1/2 hu ~ \
\ I
I
, '
iv. Classical mechanics predicts that the oscillator has a finite amplitude. This amplitude may
be calculated as per follows:
From equation 4.23
I
E
v
= kA
2
2
... (4.31)
q'
2a)~
(
= ; eax
2
J
~
+ 2
= ~ x e 2 ax dx
1t _~
=0 (as this is odd function and integral over the whole space for odd function is zero).
70 Quantum Mechanics  A Compreh~nsive Text for Chemistry
= ~2a s 2 _2al dx 2
1t __ x e
1
 4a
Example 4.2 : Evaluate < p > for the harmonic oscillator
The normalized ground state wave function for the harmonic oscillator is
qs = (2a),Y,; e{XX
2
1t
J
~~a 2r1
< P> =  e _ax21 h. a lax
e \.IX
x ~ 1t 2m ax
= ~2a
1t
(~) S eax2 (2ax) e ax2 QX
21tl _
= 0 (as this is an odd function and integral of odd function over the whole space is zero).
Example 4.3 : Evaluate the expectation value of the kinetic energy < T > for the harmonic
oscillator
As for harmonic oscillator ground state normalized wave function is
~2a _ax21 h a
2 2
= 1~
+
e
2 hv
81t 2 m ax 2 ellX dx = 4
Example 4.4 : Evaluate the expectation value of the potential energy <v> for the harmonic
oscillator.
As for harmonic oscillator ground state normalized wave function is
.'¥ = (2a),Y,;
 e{XX
2
1t
Quantization of Vibration Energy . 71
< V> = J
_~ v:;
[2a 2
e ax'l! kx 21 e ax dx
i
On solution it provides the value of <V> as
hv
<V> = 
4
Here in the case of harmonic oscillator the expectation values of kinetic energy and potential
energy are same
hv
i.e. <T> =<V>=
4
This equality is a special case for the virial theorem, As according to this theorem if potential
energy of the particle is in the form of equation V = C X n where C is any constant, the kinetic and
potential energies are related to each other by
2<T> =n <V>
For harmonic oscillator V = liz kx 2
So, n = 2 here, therefore
<T> = <V>
1. Find out frequency of an oscillator based on classical mechanics (See section 4.1)
2. Prove that V =liz kx 2 for an oscilaltor based on classical mechanics (see section 4.1)
3. On the basis of classical mechanics, prove that Etot for the oscillator is I/Z K A2 (See section 4.1)
4. Show that the energy levels in harmonic oscillator are equally spaced. (See section 4.2)
S. What do you understand by zero point energy? (See section 4.2)
6. Find out expression for amplitude for a harmonic oscillator (See section 4.2)
7. Plot 'I' and '1'2 for harmonic oscillator (See section 4.2)
8. Show that the force constant is k =4n2 mv 2 in case of harmonic oscillator
SYNOPSIS
Section Topics
5.1 Classical treatment for rotational motion of particle
5.2 Quantum mechanical treatment for rigid rotator
Rotational motion is another type of basic motion which is of great interest in atomic and
molecular problems. It sets up in atom/molecule whenever its motion is under the influence of
central field of force. For example, motion of electron around the nucleus is also rotational motion.
For a single particle which is in such type of motion Schrodinger equation can be solved exactly.
One such type of problem i.e. rotational motion of a particle in one plane (particle in a ring) has
been included in Chapter  3 (Section 3.5) therefore, rotational motion in three dimension is dealt
here with.
1 1
T = "2mlvl2 + "2m2v22 ... (5.1)
1
=T =Yz m "(r (()2 + 2 m (r 2 2
(()2 ... (5.4)
=Yz(mr , , +m 2 r , )(()
2 2
... (5.10)
rr
m,
c 8m2
I  mJ ( m 2r J2 +m2 (mJ r J2
(m, + m 2 ) (m, +m 2 )
= (mJm/ m J+ m 2 )r2
Or 1=~r2 ... (5.11)
Where ~ is the reduced mass and by defiQition
1 1 1
 =+ ... (5.12)
Il m, m2
Angular momentum of such system is given by
L = 100 ... (5.13)
1 (Iooi
= T = Y2 1002 =    [:. L = 100]
2 I
L2
Or T= ... (5.14)
21
Classically, the kinetic energy of the rotator can have any value as 00 can possess any value.
This is not true in quantum mechanical framework. Energy of rotator quantized is shown in the
next section.
Example 5.1 Show that for rotation motion v = roo
The angular velocity of a particle rotating around an axis is defined as the number of radians
swept out by the particle in a second. For one complete revolution angle 21t radians is swept by the
rotator. If v is the frequency of rotation (cycles/second)
00 = 21t v ... (5.15)
Distance covered by the particle in one complete revolution is 21tr (i.e. equal to circumference
of the rotation motion). Therefore, linear velocity of the particle is given by
v = (21tr) v ... (5.16)
From equations 5.15 and 5.16
00 v
v= andv=
21t 21tr
00 v
... (5.17)
= 21t = 21tf
= v=roo. ... (5.18)
Example 5.2 Show that for rotation motion L = 100 considering a rigid body rotating about an
axis.
Let 00 be its angular velocity. Considering ilh particle going in a circular rotation with radius
r, with its plane perpendicular to AB. The linear velocity
Quantization of Rotation Energy 75
... (5.24)
Where PI & P2 are linear momenta for the particles of rigid rotator. For freely rotating rotator,
potential energy is zero, hence total energy is equal to the kinetic energy. So,
E=
(p;, + P~, + p;\) (P;2 + P~2 +
+ ''~
P;2 ) ... (5.26)
Or
2m\ 2m2
Where p:s, p;s and and Pz's are the three components of the linear moments, of rotator along x,
y & z axis. Replacing p's with quantum mechanical operators
~~ 2
2 2 2 2 2 2
a a
a ] h [ a a a ] ... (5.27)
ax~ + ay~ + az;
A [
2
Hop = 8lt ml 8lt 2m 2 ax; + ay; + az;
It is convenient to express rotation in forms of internal coordinates
x = x 2  Xl
Y =Y2y\
Z =Z2  Zl ... (5.28)
76 Quantum Mechanics  A Comprehensive Text for Chemistry
2 2
As a (a)2 [ax a]2 [ a J2 a ... t5.29)
axi = axI = axI ax = (I)ax  ax2
a2
a 2
... (5.30)
... (5.31)
2 2 2 2
_h [a a a ]
Or
= 81t2~ ... (5.32)
A
H op
A = '¥ =E'¥
=> _h
2
[a a
d ]
2
2    +  +  '1'= E'¥
81t ~ ax 2 dy2 dZ 2
2 2
... (5.33)
Expressing x, y, z in terms of Polar coordinates i.e. r, e & <I> for which '¥ is function of r, e & <I>
WM~~r,~.y
,,
,,
x
... (5.35)
... (5.36)
In the above equation (5.36) \}' can be replaced by Y (a. <1» i.e. spherical harmonics and equation
5.36 can be rewritten as
_h2
41t2
[_.I_ a
smS a S
(sinS~)++;]Y(S'<I»=(2EI)Y(S'<I»
a sm Sa<l>
... (5.37)
h
U = J (J + 1) (2 1t J ... (5.40)
Where J is the rotation quantum number. Therefore. energy for the rotator E is given by
2
E=~=J(J+l) 1(h )2
21t 21 21t
h2
Or E = 81t 2 I J(J +1) ... (5.41)
1.  a
 ( sma
. a) +'22
1 a] Y(a.<I»=J(J+l) (h)2
 Y(a,<I» ... (5.42)
[ sma aa a<l> sm a 0<1> 21t
Or
2
a (' ay) a y
sin a aa smS a<l> + J(J+ 1) sin2 ay + aq,2 =0 ... (5.43)
Z
a (. ae) a $
<»sine ae smSa$ +J(1+1) sin2 ee+e a$z =0 ... (5.45)
e sine aa (sin S
e ~:) + J(1+1) sin e = m
2 2
... (5.47)
In this way equations (5.47) and (5.48) are two resolved equations for Schrodinger equation set
up for a rigid rotator.
Soilition of <\I equation (5.48)
Since the <» equation is
21t
Or N f exp(im<»)exp(im<») d<» = 1
o
or AZ (21t) =1
Quantization of Rotation Energy 19
1
A2 = 
21t
1
Or A= ... (5.52)
21t
Incorporating the value of A
1
<l>m = fiit (exp im <1» ... (5.53)
0
Yfiit
+1 Yfiit exp (i<l»
p1 [(1X 2
)]
d [ 2 dP]
dx (IX) dx +J (J +1) (1 X) =m
2
... (5.57)
80 Quantum Mechanics  A Comprehensive Text for Chemistry
Or
2 2
(I_X2) d p  2x .E.
d  [ J(J+l)2
_m ] p=o ... (5.59)
dX dX IX
Equation 5.59 is called as associated Legendre equation. Solution P of the associated Legendre
polynomials are given by :
d'm'p
P = PIIml' = ( IX 2)Irnx _ _I
dXhn' ... (5.60)
p~rnl is associated Legendre polynomial of degree J and order m. Pj in equation 5.60 is Legendre
polynomial and is given by
l
I d I
PI = 21J! dxl (X21) ... (5.61)
Solution of P of the function e also requires Iml ~ J for finite function. The two quantum
conditions therefore are
J = 0, 1,2,3,
and m = 0, ± 1, ± 2, ± 3 ... (5.62)
Therefore, m can have (2J + 1) values for a given value of J. After mmualization 8 is given by
U = J (1+1) (2~ J
Or U =J (J+l)(Ii)2 ... (5.64)
[Where Ii = hl21t]
This implies that J quantum number is responsible for quantization of total angular momentum
of the rotator. Similarly J is also responsible for quantization of E, the rotational energy as
h L:
E =J (1+1) 81t2I or 21 ... (5.65)
... (5.66)
Equation 5.66 implies that z component of the angular momentum has precise value as given by
h
L z =m  ormli ... (5.67)
21t
Hence, m quantum number gives the quantization of angular momentum and can have values
0, ±1, ±2 ........ ..
As
Since
U =L2+L2+L2
x y z
=> UL2 =L2_h 2
z x y
... (5.69)
R.H.S. of above equation will be a positive quantity. Therefore, L.H.S. of equation 5.69 should
also be positive quantity.
82 Quantum Mechanics  A Comprehensive Text for Chemistry
Or
EJ =J(J+1) (2:)2 ;1
h2
Or EJ = 8n 2 I J (1+1)
J =0 Eo =0
J = 1 E( = 2h 2/8n 21
J = 2 E 2 = 6h 2/81t21
J = 3 E3 = 12h2/81t 21 and so on
Above calculation ofE J for different J levels show that spacing between rotational levels increases
with increase in rotational quantum number J.
1. Show thal for a rigid rotator T =Y2 1002 on the basis of classical mechanics (See Section 5.1)
2. Prove that 1== W for a rigid rotator (See section 5.1)
3. Prove that for rotation motion v =rOO (See section 5.1 example 5.1)
4. Set up ~'_hrodinger equation for a rigid rotator (See section 5.2)
5. E .:::ai(: ':artesian and polar coordinates and write Schrodinger equation for a rigid rotator in terms of
tJv;.H coordinates (See section 5.2).
6. What do you understand by spherical harmonics? (See Section 5.2)
7. ""rite a note on physical significance of 1 and m. (See section 5.2).
8. Discuss the solutions of e and <l> part of wave function or spherical harmonics for rigid rotator (See
~ectlOn 5.2l.
9. Sho~ lilat Er==O for 1=0 i.e. energy of minimum or zero level for rigid rotator is zero. (See example 5.3).
10. ProVt that spacing between rotational levels increases with increase in rotational quantum number 1.
\:~c" ('x ample 5.4).
______________________CHAPTER6__ ~ __________________
SYNOPSIS
Section Topics
6.1 Schrodinger wave mechanical treatment for Hatom
6.2 Acceptable solutions for <I> (<I» equation
6.3 Acceptable solution for e (0) equation
6.4 Acceptable solution for R (r) equation
6.5 Energy of Hatom
6.6 Energy in atomic units (a.u.)
6.7 Quantum numbers and their significance
6.8 Total wave function for Hydrogen like atom
6.9 Radial probability distribution functions (RPDF)
6.10 Shapes of atomic orbitals
6.l1 Energy levels and degeneracy of orbitals
6.l2 Spectra of Hydrogenlike atom
6.13 Electron Spin
Hydrogen is a simplest of all chemiCal systems. It provides the model for the study of atomic
structure in general. N. Bohr had also tried to explain the hydrogen atom and his mathematical
framework was based on the basic assumption of quantization of orbital angular momentum of
electron. This theory provides a basis for quantization of energies and to explain the experimental
features of hydrogen  like atoms as H, He+, a?+ and IBe3+ etc. This theory, however, failed to
explain the relative line intensities in the hydrogen atom and it also failed to explain energies and
spectra of complex atoms. In this chapter, quantum mechanics for Hydrogen like atoms is discussed.
83
84 Quantum Mechanics  A Comprehensive Text for Chemistry
e, e
= r;;::;: . SI umts.
10
.
"\j 41tE o
... (6.3)
... (6.4)
and
... (6.5)
Equation 6.4 is associated to movement of centre of mass of Hatom system and E trans is
translational kinetic energy. Equation 6.5 corresponds to motion of electron W.r.t. to stationary
nucleus and e is electronic energy here with Ile is reduced mass. As this equation is the only equation
which is concerned with motion of electron so, solution ofthis equation is discussed here only. This
equation can be transformed into equation in terms of spherical polar coordinates i.c. r, e & <I>
using relations.
Hydrogenlike Atoms 85
x = r sine cos<l>
y =r sine sin<l> .. (6.6)
z = r cose
Result of this transformation is
2
h2 { a
:'~ ( r 2a ) + 1  a ( sma
. ' 1 a ]  ze,2]
a )+   'I'=E'I'
2 2
[ 81t Jlr ar ar sin a aa aa sin 2a a<l>2 r
... (6.7)
... (6.9)
 1 d ( r 2 
dR(r»)
 + 1 d (. sma d0 (a») +
R(r) dr dr 0sina da da
1
2
d <1>(<I» 81tJlr2 ( Ze,2)
<1>(<I»sin 2a . d<l>2 +. h2 E + 7 =0 ... (6.11)
Or
2
_1_.! (r2 dR(r») + 81t\Lr (E + Ze,2) = I d (. d0(S))
R(r) dr dr h2 r 0(<I»sine da sm e de
Both the sides of equation 6.12 are equal to one constant I (l +1) (say). Therefore, this equation
can be separated into (i) Radial equation (involving radial part of function).
2 2
_1_ .! ( 2 dR(r») 81t Jlr ( Ze,2)
R(f) dr r dr + h2 E+r  =1(1+1) ... (6.13)
and
(ii)The angular equation (involving angular part of the function).
2
1 d (. d8(S») I d <1>(<I»
0(S)sinS dS sm SdS + <1>(<I»sin 2 S d<l>2 =/ (l + 1) ... (6.14)
Equation 6.14 can be further separated into two equations involving S & <I> parts of the wave
function. For this purpose, multiply this equation by Sin2S and rearrange it.
Both the sides of equation 6.15 are equal to a constant m 2 say. Therefore, we get
sinS d (. d8(S») 2 2
0(S) dS sm S d S + 1(l + 1) sin S = m ... (6.16)
And
1
=_m2 ... (6.17)
<1>( <1»
So, Schrodinger equation for Hatom can be resolved into three equations viz.
...(6.13)
1
... (6.17)
<1>( <1»
The acceptable solutions of these equations provide the information for R(r) 8 (S) and
<1>(<1» parts of wave function and energy of electron can be obtained from R (r) equation i.e.
equation 6.13.
Hydrogen like Atoms 87
1
=_m2
¢>(<I»
Its acceptable solution has already been discussed in chapter 5 in case of a rigid rct"tor It~.
acceptable solution is
1
<l>m = .fin exp (im <1» ... (6 18)
as ~eXP(im<l»] = ~
(t 2 ) [ ,,21t 2m
~ [ ~ eXP(im<l»]
a<l> ,,21t
... (6.JCl!
or it is equal to
= mh [ ~
21t ,,21t
eXP(im<l»] ... (6.20)
Therefore, the permitted L z values for moving electron i.e. \';Jues ['.'r z:cHnponents of angular
momentum of electron are m Ii or mh/21t.
8sin d (. d8(e»)
   s108 + I (l + 1) sin2 e = m 2 ... (6.16)
(e) de d8
The acceptable solution for this equation as per rigid rotator problem i'>
~
8
1
,m
=
[
(2! + 1) (IIml )!
2 (l + I mI )! ] pim' ... (.6.21)
... (6.27)
or
... (6.27)
Using suitable transformation it is possible to write this equation in most familiar form known
as associated Laguerre Equation
2
d2
P2  L + (j +1p ) 
dL+ (k J.) L= 0 ... (6.28)
dp dp
... (6.35)
Hydrogen like Atoms 89
j R(;) R(r)r dr =1 2
... (6.40)
o
we get
R {( 2Z )3 n 11 }Yz pI p/2 L21+1
... (6.41)
= na o 2n[(n + I)!f e n+1
41t/lze,2 )
where p = (2 ar) = 2 ( nh 2 or = ... (6.42)
The constant n is referred to as principal quantum number. Tht: as",ociated Laguerre polynomical
is not to vanish, we have
j~k ... (6.44)
Or (21 + I) ~ (n + 1) ... (6.45)
[as J = 2L+ 1
and k = n+1J
or 1+I~n ... (6.46)
or l~nI ... (6.47)
The principal quantum number n may be any positive integer
n = 1,2,3,4 .. (6.48)
so allowed values for I are
1 =0, 1,2 ...... (nI) ... (6.49)
90 Quantum Mechanics  A Comprehensive Text for Chemistry
... (6.33)
4n2/lze ,2
a = Ah2 ... (6.34)
or =
This energy expression in identical with the energy expression as derived by Niel Bohr in
Bohr's Theory.
... (6.13)
... (6.50)
Hydrogen like Atoms 91
a _ (41t~\I)h)
( 0  41t2me2 0.529 x lO iOm 1 a.u
_Z2
and E=2 ... (6.52)
211
In case of Hatom Z = 1 therefore
1
E = 2"a.u.
1 dr
 2 d (2
[  e r)] _2e r
2r2 dr dr r
r
= 1 d [ (2r 2e)
r ] 2e
 ... (6.53)
2r2 dr r
1 2e~ 1
= 2r2 [4re
r
+2r2 e r ] r =  2" (2er ) ... (6.54)
or ... (6.50)
(c)Magnetic quantum number (m) decides the magnetic orientation of moving electron in
any orbital or it decides about ascertaining the value of zcomponent of angular momentum of
moving electron as L z value m 1i or mh/21t.
1 'I'1,0,0
1
2 UI
T (2,0,0) = ..J321t Z3/2 (2 Z)r eZrI2

'I'
(2,1,0)
= _1_Z5I2
..J321t r eZJ:12 cose
'I' = _1_'_Z5/2reZJ:/2sineeiejl
(2,1,1) ..J641t
Or
Plots of radial probability distribution functions on the basis of a.bove equations 6.58 or 6.59
are given in fig. 6.1 for various orbitals. These plots provide the information of probability of
finding electron within the spherical atomic space of radius 'r'.
t
u..
Cl
15
a..
a::
r .
2p
t
u..
Cl
25
a..
a::
3d
t
u..
Cl
35
t t
u..
Cl
a..
a.. a::
a::
r. 4p r.
t
u..
Cl
t tI
a..
a::
'n' in the RPDF plots denote the points where the probability with radius becomes zero. These
points are known as nodes. Presence of nodes in RPDF plots shows that in atomic space of radius
'r' these are regions where probability of finding electron becomes zero. Taking example of plots
for Is and 2s orbital set, presence of one node in RPDF plot clearly indicates that within the atomic
space of radius 'r' after maximum electron density of 1s orbital there is a space where probability is
zero, this region is node and after that 2s orbital has maximum probability for electron. In brief this
Hydrogen like Atoms 95
can be concluded that Is is inner orbital and after nodal space there is 2s orbital as shown in
figure 6.2.
Fig. 6.2
Above equation explains that at e=nl2 i.e. at xy plane probability of finding electron is zero.
Therefore, this can be concluded that orbital is distributed on zaxis above and below xy plane.
Function of 2pl is independent of <I> part. Therefore, this may be concluded that shape of 2pz is
dumpbell with +ve and ve lobes. Similarly, this can be shown that in case of 2px and 2py orbitals
yz and xz are the nodal planes. In case of atomic orbitals it is a significant fact that in their shapes
'¥ is ve also. This may be significant as '¥ is not at all important but it is ,¥2 or '¥'¥* which is
significant.
In case of dorbitals (where 1= 2) the study of spherical harmonics shows that dorbital set is a
superimposition of two orbitals and it contains four electron density areas which are separated by
two nodal planes. Shapes of s, p & d orbitals are given in fig. 6.3 as it is complicated to explain the
shapes of f and g orbitals.
96 Quantum Mechanics  A Comprehensive Text for Chemistry
y
z
y y
y
7IIf~~X
~~~+x
Plorbital
p.orbital
z y
z
~~+<~.x ~~~~x
dxzorbital
z
x
~~~~y
x dyzorbital
dx'/ orbital
... (6.61)
Therefore, no. of orbitals (or wave functions) having same value of energy is n2 in case of
hydrogenic wave functions. For n = 1 these are non  degenerate wave functions and for n=2 wave
functions are with 22 fold degeneracy and so on. The energy levels diagram with the relative
degeneracy of orbitals is shown in figure 6.4
... (6.50)
or ... (6.62)
n 5 p d
4
45(1) 4p(3) 4d(5) 4f(7)
3
35(1) 3p(3) 3d(5)
2
25(1) 2p(3)
15(1 )
Fig. 6.4 Energy level diagram for atomic orbitals for Hatom
98 Quantum Mechanics  A Comprehensive Text for Chemistry
... (6.64)
The fate of a transition can be decided on the basis of selection rules which can be framed on
the basis of transition moment integral i.e.
(6.65)
A
where \1'1' & \1'2 are wave functions of two different electronic states and if J.1 is dipole moment
operator. For allowed transition the integral given in equation 6.65, this should have value one or
finite value but for forbidden transition this integral should have value zero. Therefore, the selection
rules for Hydrogen like atom are
(i) An = (n 1  n 1) = any integer means A n can be any integer thus reproducing all the spectral
lines of Hatom i.e. Lyman, Balmer, Paschen series, etc. This rule is in accordance to
Bohr's postulate of transition between two energy levels.
~
.1
~1 I" f1
Humphery
~ Ir
"
Pfund
t11r Brackett
.1 hlr Pschen
.Lyman
hlr Balmer
Given
At nucleu~ r=O
Z3 )Yz]2
I'¥IJ = [( 1ta~
=2.15 x 106 Z3 nm3
If Z = 1 as in case of Hatom
I'PIP = 2.15 X 106 nm· 3
Example 6.2 : Making use of the 'P Is given in example 6.1. Prove that for Hatom in such a
state the most probable distance from the proton to the electron is au.
For s orbital
For
And in case of Hatom Z=1
'illS =(1ta30)·1I2er/au
So, applying rule of maxima for must probable distance.
100 Quantum Mechanics  A Comprehensive Text for Chemistry
Or (41tJ
3
ao
e 2r/o
0
[2r 2r2]
 =0
ao
In above equation since exponential function cannot be zero therefore, the tenn in [ ] square
bracket will be zero
2r2
=2r ao =0
=2r= ao
Or r =ao Hence proved
Example 6.3 : Predict that transition from 3d to 3p will be allowed or forbidden.
According to selection rule (i) An = any integer for electronic states involved in a transition
For transition 3d ~ 3p, An is not an integer.
According to selection rule (ii) Al =± I for electronic states involved in a transition and according
to selection rule (i.ii) Am = 0, ± I. Therefore, transition 3d ~ 3p may be allowed if and only if Am =
0, ± I i.e. change in magnetic quantum number should be either zero or ± 1.
'44·]:183*.,411
1. Set up and write Schrodinger wave equation for Hatom (see section 6.1).
2. Write three simpler resolved equations for Hatom in tenns ofR(r) 9(9) & $(cp) (See section 6.1)
3. Discuss the acceptable solution for cp ($) part equation (See section 6.2).
4. Discuss acceptable solution for (9) part of equation as set up for Hatom (see section 6.3).
5. Give acceptable solution for R(r) part of equation as set up for Hatom (See section 6.4).
6. Derive the expression for energy for Hatom (See section 6.5).
7. Derive the expression for energy for Hatom in atomic units (a.u)(see section 6.6).
8. What are quantum numbers? Give their significance (See section 6.7).
9. Write about orbital angular momentum of electrons (See section 6.3).
10. Write total wave function for Hlike atom (See section 6.8).
11. Write a note on Radial Probability Distribution function. What is the significance of RPDF ?
(See section 6.9).
12. How can shapes of different orbitals be explained (See section 6.10).
13. Discuss the energy levels and degeneracy of atomic orbitals. (See section 6.11).
14. Explain the spectra for Hlike atom. (See section 6.12).
15. What do you understand by electron spin? (See section 6.13).
SECTION3
7. Introduction to Approximate Methods
8. Variation Theorem and its Application
9. Perturbation Method and its Application
10. Introduction to Angular Momentum
11. Electron Spin and Related Cconcepts
"This page is Intentionally Left Blank"
______________________CHAPTER7______________________
SYNOPSIS
Section Topics
7.1 Variation Theorem
7.2 Perturbation method
7.3 Introduction to multi electron system
Exact solution for Schrodinger equation as set up for a oneelectron system is possible. Even
this solution is possible with lengthy mathematical calculations. This difficulty is because of presence
of potential energy term in the hamiltonian for single electron system there is only one potential
energy term viz.  Ze 2/r. In case of multielectron system, electron and nuclei interact with each
other as a result of which many potential energy terms may be included in Hamiltonian operator or
such systems. For simplicity in such cases one has to make use of approximate methods for
calculations. The important and significant approximate;methods are (i) variation theorem and (ii)
perturbatioq. method.
103
104 Quantum Mechanics  A Comprehensive Text for Chemistry
Schrodinger equation is
... (7.9)
Hcjl, =Ecjl,
Similarly Hcjl2 = E2 cjl2 ... (7.12)
and
_h2 d2 1
H= 81t2m dX2 + '2 kx2 ... (7.17)
If perturbed state of the oscillator is taken into account the hamiltonian will be
_h 2 d2 1
H = 
~   +  kx2 + ax3 + tx4
81t 2 m dX2 2
... (7.18)
And
E = E (0) + AE (1)+A2En(2) ... (7.23)
n n n
Where 'I'n(k) and En(k) are the kth ?rder correction terms in '1'0 and Eo respectively. In most of the
problems in chemistry we go upto 'I'(2)n and En(2)· usually..
Therefore
= (H o+II.H
A'I 'I UJ (I)
'I'o+II.T
A ')( 'I (2)UJ (2)
n +11. Tn + ....... .
)
'1E(I)
 (E0+11. 'I (2) E(2)
n +11. + ...... ) (Ul 'I Ul(l)
TO+II.T 'I (2) (2) ) (7 24)
n +11. "'n + ........... .
On rearranging the equation 7.24 we get
(H0
'I' 0
E0'I' ) + A(I) (Ho '1'(1) 'I' (I) _ EO
n + H\}Ion _ EOnn )'I'(O») +
nn
... (7.25)
And so on so forth
Equation 7.26 represents Schrodinger equation for unperturbed state and equation 7.27 and
7.28 are equations for first & second order perturbations respectively.
Usually first order corrections/perturbations are employed to get corrected values for wave
function and energy. These correction terms are as under:
First order correction to energy :
As first order equation is
... (7.27)
... (7.29)
As H is Hermitian operator
J'P()n
* Ao 'P(\)d't
On
= J'P*O) AOn'P°d't=
n
J'P*(l)
n
E(O)
n
'P°d't
n
J'P°*A''P(i)d't
nOn
= E(I) J'P(O)*
n
'P(O)d't=O
n
Or ... (7.30)
... (7.31 )
Or ... (7.32)
R
12
... (7.34)
Schrodinger equation is
... (7.43)
1. What is the need of approximate methods in quantum mechanics? (See section  introduction
of chapter).
2. What is variation theorem? (See section 7.1)
3. What are the steps of application of variation theorem? (See section 7.1)
4. What is perturbation method? (See section 7.2)
5. What do you understand by first order and higher order perturbations? (See section 7.2)
6. Discuss the independent electron model for Heatom. (See section 7.3)
_______________________ CHAPTERB ______________________
SYNOPSIS
Section Topics.
8.1 L.C.A.O.M.O. Theory for H/ molecule ion
8.2 Application of variation theorem to Heatom
Approximate methods viz. variation principle and perturbation method have been introduced
in chapter 7. Need of such methods in quantum mechanics has also been focused in the same
chapter. In this chapter contents related to variation theorem and its application with its use in
multielectron system is being discussed.
As it is introduced in section 7.1, the linear variation theorem states that with any trial function
'I' the expectation value of energy E will be greater than the true value Eo which is the lowest
energy eigenvalue of the Hamiltonian operator of the system.
E~Eo ... (8.1)
Proof of this theorem has been introduced in section 7.1 and it is mentioned that according to
one of the postulate of quantum mechanics average energy ofEigen values for the equation .
E = J"lH'I'd't •• , (8 ~
I)
>
J'I'* 'I'd't
Molecular orbital theory may be taken as one of the applications, of variation theorem. In the
next section, molecular orbital theory or LCAOMO concept is given.
... (S.4)
A~~
... (8.6)
... (8.7)
... (8.8)
C~aA+C;aB +2CICZ~AB
E = z Z
C I + C z + 2C IC ZS AB
... (8.14)
The integrals a A & a B are Coluomb integrals. The values of a A & a B are close to EA & EB
where EA & EB represent the energy of an electron in '¥A and '¥B in isolated Hatoms. The integral
~ AB is resonance integral whose value is the measure of exchange of an electron from one atom to
another. It is also known as exchange integral and has a negative value always. The integral SAB is
known as overlap integral and is a measure of the extent of overlapping of two atomic orbitals. To
optimize the coefficients C I & C 2
dE dE
 =Oand  =0 ... (S.15)
dCI dC z
Equation 8.14 may be rewritten as
Differentiating it w.r.t. C I
(:~J
2C l a A + 2C2~ AS  2E(C I + C 2 S AB)
Or ... (8.18)
C~ + C; + 2C IC 2 SAB
Putting (dE/dC I ) = 0
ClaA+C2~AB  E (C I + C 2 SAB) =0 ... (S.19)
Similarly. from (dEidC 2 ) = 0 we get
... (8.23)
For non zero solution the first determinant must be equal to zero i.e.
...(8.24)
Equation 8.23 is known as secular equation and determinant in equation 8.24 is known as
secular determinant. On expansion of this determinant
(a A E)(aBE) (~AB E S AB)2 = 0 ...(8.25)
As here we are dealing with H  atoms viz. HA & HB therefore
aA = aB = a ... (8.26)
So equation 8.25 may be expressed as
(aE)2  (~AB  ES AB)2 =0 ... (8.27)
Or 0. E =± (~AB  E SAB) ... (8.28)
Which implies that two values of energy may be obtained which are
E1
 (a+~AB)( ) ... (8.29)
 /P+SAB
... (8.32)
1
Or C  r==:====:= ... (8.37)
1  ~2(1 +SAS)
Similarly C 2 will have the value
... (8.38)
El & E2 energies for the M.O.'s can be compared simply by taking SAB = 0
=> EI = a + ~ AS and
E2 =a~AB ... (8.39)
Both a & ~ AB are negative, therefore
EI <E2 ... (8.40)
Which shows that m.o. '1'1 will have lower energy than '1'2. Their display on energy level
diagram gives us the M.O. diagram for H/  ion.
I
I
'112...,
I
I \
I \
I \
\
I \
I \
® I
\
I \
\
I
'¥A \
\ I
I 'liB
\ I
\ I
\ I
\ I
\ I
\ I
\ I
(1) I
'¥,mo
_h _e2 _e e [ 2 2 2
a =<'1' _ _ \7 2 _ _ +_ 'I' > ... (8.41)
'A 2 A [81t m rl r2 R A
Or
Variation Theorem and Its Application 115
2 2
h  2 e e 2 e
2
UA =<'¥A 2V  +'¥A >+<'¥A  2 '¥A > +<'¥A  '¥A> ... (8.42)
81t m r1 r R
In the above equation, the first term is equal to the energy of 1s orbital of an isolated Hatom.
As R is internmullear distance, so, third term is equal to e2/R. Second term is coloumb integral
J, so,
... (8.45)
Or
... (8.46)
Or ... (8.47)
Where K is actually known as exchange integral and it represents the exchange of electron
between A & B atoms.
SAB integral may be expressed as
SAB =<'¥AI'I'B> ... (8.48)
... (8.49)
... (8.50)
M.a. expressed by E\ whose energy is smaller than that of isolated A.a. is known as bonding
M.a. and M.a. which is expressed by E2 is anti bonding M.a. If an electron is placed in bonding
M.a., it will increase the stability ofthe molecule if and only if electron is placed in antibonding
M.a. it will make the molecule ion less stable.
Wave functions for the M.a. is viz. '1'\ & '1'2 can be taken into account for the'probability
distribution as
~~~~~~~
,,
,,
,,
,,
, ,
" ...
......
~~~~~~~~
Variation Theorem and Its Application 117
_ 2 _ I\}1I H I\}1dt
... (8.55)
E. s  J\}12dt
If\}1 is normalized wave function
J\}12dt=1 ... (8.56)
Which implies that
= E 1s2 =JJ Is(1) Is(2)\H(1)lls(1) Is(2)dt. dt2 + If Is(l) IS(2)\H(2)\ Is(1) Is(2) dt.dt 2 +
Where \}1He = \}1 = Is(l) Is(2) involving 2 electrons in Is orbitals and Hamiltonian may be
written as
H = H (1) + H (2) + !where H (I) and H (2) are hamiltonia for electron 1 & 2 and
R
l/R is the interaction term
ElS2 = If Is(1) Is(2) E~c (1; ls(l)1s(2) dt. dt2 + If Is(l) Is(2) E~c (2) Is(l) Is(2) d't. dt2 + J ... (8.60)
Therefore E
 Is2 = 2Els II [1s(1)ls(2)] d't. d't2 + J
2 ... (8.61)
E = Ils[.!.V2
Is 2
 Z] Is dt
R
... (8.63)
118 Quantum Mechanics  A Comprehensive Text for Chemistry
27
=z'= ... (8.70)
16
Therefore, the value of
E IS
2 _

(27)2
16
_(27)
8
(27)_ ..
8   2.84 atomIc umts.
Or 77.48 ev or  1.24 x 10 17 J. This value of energy is almost near exact value energy of He
atom
SYNOPSIS
Section Topics
9.1 Particle in one dimensional box with perturbed potential energy
9.2 Application of perturbation method to Heatom
One approximate method viz. variation principle has been discussed in chapter 7 and its
applications are given in chapter 8. Perturbation method is also another approximate method which
is being used in quantum mechanics to get near exact values for energies, eigen values and wave
function etc. This method has also been introduced in chapter 7. In this chapter contents related to
applications of perturbation method with its use in multielectron system are being introduced.
As it is given in section 7.2, the perturbation method is applied if the system differs slightly
from unperturbed state and if energy (Eo) and the wave function ('Po) for the unperturbed state are
known. The perturbation theory involves the determination of the Eigen function ('P n) and Eigen
values (En) corresponding to the perturbed Hamiltonian (fI') in terms of ('Po) and (Eo) related to
unperturbed Hamiltonian (H 0 ). It has also been introduced in the same chapter (section 7.2) that
first order corrected energy is given by
... (9.2)
119
120 Quantum Mechanics  A Comprehensive Text for Chemistry
~ H'mn 'Po
Or £.J EO EO m ... (9.3)
m*n n  m
In this chapter two applications of perturbation method viz. particle in onedimensional box
with difference in potential energy and application of perturbation method to Heatom are given.
ux
. V(x);::: ... (9.4)
L
At x =0
V(O) = 0 and at
x =L V(L)=u
Change in V(x) in the box can be expressed as per figure 9.1
x=o
Fig. 9.1
Zero order energy for the particle is n2h2/8mU. First order corrected energy after the perturbation
can be evaluated as
...(9.5)
Perturbation Method and Its Application 121
Or ~= Jf sin ( 1l~ )
E (I) = 2 x 
U fL . 2 (ll1tx)
xsm  dx ... (9.7)
n L L 0 L
2 U L2 U
Or E (I) ::::  X  X  = ... (9.8)
n L L 4 2
... (9.9)
Similarly, wave function after perturbation i.e. first order corrected wave function may be
;;alculated as
h2 4h2
... (9.13)
Et  E2 = SmL2  SmL2
On substituting values from equations 9.12 and 9.13 in equation 9.10 & on solving it, the
correction tenn will be
122 Quantum Mechanics  A Comprehensive Text for Chemistry
... (9.14)
Incorporating this first order corrected wave function total corrected wave function w.ill be
~ . (1tx) + ~
2
'II =  sm 32L
  u sm
. (21tX)
 ... (9.15)
L L L 271t4 L
... (9.16)
Where H0 is the Hamiltonian for zeroth state i.e. it is the Hamiltonian for electron 1 and
electron 2 in Is orbital of Heatom.
A A 1 A
As <1>(1) and <1>(2) are normalized functions, Let us suppose EO) = J where J is average columbic
.
energy term for Heatom m ground state J = 8"5 Z
5
J =Z ... (9.20)
8
Therefore, for Heatom total energy with first order corrected energy will be
 5
E 2=_Z2+Z ... (9.21)
Is 8
1
As 'Ills for Hatom (in a.u.) = In exp (r) (as '11 1(0»
Therefore
Hence, first order corrected energy has value equal to zero. Therefore, there is no first order
effect in this case.
SYNOPSIS
Section Topics
10.1 Introduction to angular momentum
A A ...
Angular momentum, a physical property, has a lot of significance in quantum mechanics. This
property was used by Bohr in his atomic theory (see postulates of Bohr's theory, section 1.7).
While discussing the properties Qfa rigid rotator angular m.1mentum has been introduced in context
to quantum mechanics (See section 5.2). In this chapter, quantum mechanical concepts related to
angular momentum starting from the introduction of angular momentum have been included.
124
Introduction to Angular Momentum 125
Where L2 is the square oftotal angular momentum of moving electron. For a rigid rotator this
can also be shown that for L2 and Lz operators there exist some Eigen values. Here U is the total
angular momentum operator and L z is z component of angular momentum. When these operators
are operated on spherical harmonics, Y (9, cjl) for a rigid rotator we get the following Eigen
equations.
... (10.2)
This has been proved earlier that the quantum number I may have values 0, 1, 2, 3 ........... and
'm' may have values 0, ± 1, ± 2, ± 3   ± I. Siqlilar to Lz angular momentum may also have
another component Lx & Ly. These Lx, Ly & Lz components of angular momentum can be defined as
per the following equations.
Lx =y pzz Py ...(10.3)
Ly = z PxxPz ... (10.4)
and L z =xPyy Px ...(10.5)
On the basis of classical mechanics Let om' be the mass of a particle and Let this particle is
moving around origin i.e. '0', then angular momentum (L ). May be defined as rxp
i.e. L = rxp ... (10.6)
i Jk
x y z ... (10.9)
Px Py Pz
Or ... (10.10)
d
Px = ... (10.12)
dx
n d
... (10.13)
Py =i dy
n d
... (10.14)
pz=
dz
[where n = hl21t]
Implies that
_ n
Lx =.
1
[ y~z~]
dz dy
... (10.IS)

Ly = in [ddx  x dzdJ and
Z ... (10.16)
Lz = ~i [x~y~]
dy dx
... (10.17)
Equations for Lx, Ly and Lz mentioned above are the operator form of angular momentum
components Lx, Ly & Lz.
Introduction to Angular Momentum 127
2 2 2 2
n2 d d d
y+yzyxz 2
d + z xd ]
Or  [ dx dxdz dydx dydx dydz ... (10.19)
2 2 2
d2 d d + d + d ]
. . L  n2 zyz2    x y 
A A
x  xz ... (10.20)
Similarly Ly x [ dxdz dxdy dz 2 dy dxdy
Therefore
... (10.21)
=F n [y~x~]
2
dx dy
(asF=I) ... (10.22)
= ih [~(y~x~)]
dx
I dy
... (10.23)
= in Lz ... (10.24)
Likewise this can also be shown that
[ 1,z L]=iIiL
y x
... (10.28)
Above equations clearly denotes that components of angular momentum operator i.e. Lx Ly &
Lz do not commute with each other. This fact has a significance that it is not possible to ascertain
the values of two components of angular momentum simultaneously. Therefore, this may be
concluded that at a time one component of angular momentum of a tiny particle like electron can be
ascertained.
If commutation of e and i.z operators is carried out this can be concluded that eand i.z
operators commute with each others. This clearly shows that U and i.z values i.e. square value of
angular momentum and its one component i.e. zcomponent value for a tiny particle like electron
can be ascertained.
...(10.32)
Therefore
Or [1; Lzl =0
""'2 A A A
Similarly, this can also be shown that [LyL2] and [L~L2] are also zero.
... (10.33)
i.e. i} can be commuted with 1.z operator. Likewise this can also be shown that [1.2 Lx] and [f.2 4]
also commute with each other.
~~~~~~y
~=~ dr +~ de +~ d<l>
dx dr dx de dx d<l> dx
~=~ dr +~+ de +~ d<l>
dy dr dy de dy d<l> dy ... (10.42)
~=~ dr +~ de +~ d<l>
dz dr dz de dz d<l> dz
And
Introduction to Angular Momentum 131
. d
=sinO cos~ +0 +0
dx
~ = sin 0 sin ~ + 0 + 0
dy ... (l0.43)
d
=cosO+O+O
dz
Similarly
dO cosOcos~
=~
dx r
dO cosO sin~
= r
dy ... (10.44)
dO sin 0
=
dz r
And
d~ sin ~
=
dx rsin 0
d~ cosO
=
dy rsin 0 ... (10.45)
d~ =0
dz
Lx = iii (sin~~cosocos~~)
dO d~
... (10.46)
L~ y
=ili (cos~~cososin~~)
dO dIP
... (10.47)
...(10.48)
132 Quantum Mechanics  A Comprehensive Text for Chemistry
2
"2 1 d. d ) +
= [ Ii 2 ( (sm9) 1 d ]
L sin 9 d9 2
d9 sin 9 d<l>2 ... (10.49)
Two new operators are being introduced in this section viz L+ & L_ ~perators. These operators
are also related to angular momentum. These operators can be defined as follows:
... (10.50)
...(10.51)
This shows that L2 and L+ commutation gives the result zero. Similarly, L2 and L_ commutation
will also give the result zero.
Ii (Lx + iL y )
As [LhJ'¥
= (L+ Lz ) '¥  (Lz L+ )'¥ ... (10.54)
Introduction to Angular Momentum 133
Or ... (10.55)
... (10.56)
Operator defined in equation 10.56 is step up operator. Similarly step down operator can also
be shown as follows:
Collectively, these operators which are defined in equations 10.56 and 10.57 are known as
Ladder operator.
I
<l>m = J2;, exp (im<l» ... (10.59)
L <I>
z m
 ~ ~ ~exp(im<l»)
(
21t d<l> v21t
... (10.60)
mh 1
= 21t J2;, exp(im<l»
Or ... (10.61)
Therefore, it has been proved that <l>m is an Eigen function for L z operator with eigen value L
i.e. m Ii or mh 121t. The corresponding eigen equation may be written as
134 Quantum Mechanics  A Comprehensive Text for Chemistry
... (10.63)
Taking example of spherical harmonics for I s orbital i.e. for I = I and m = 0 orbital
qs(l,Q)
3
= ( 41t
)Y: cose ... (10.64)
...{10.65)
This equation shows that '1'(1,0) is an eigen function for U operator whose U value i.e. the
eigen value is 2h2/41t2 • Therefore, equation 10.65 is an eigen equation. In comparison to it when Lz
operator is operated on qst 1.0) function, following equation has been obtained
d
Lqs(l.O) = ill d4> (cos e) = 0 ...{10.66)
Equation 10.66 shows that '1'(1.0) is not an eigen function for L z operator.
...{10.67)
Or ...{10.68)
Which shows that the Eigen value for L2 operator i.e. L2 value is 1(1+ 1) 11 2 or the value of
total angular momentum for electron is given by
Since L2 = 1(1 + 1) 112
=L= ../1(1+1) 11
h
Or ... (10.69)
L = ../1(1 + 1) 21t
Equation 10.68 is an Eigen equation. In this way it is clear that on the operation of L z operator
value ofLz and on the operation of (2 operator value ofU can be obtained. These are significant
Introduction to Angular Momentum 135
results. Relation between Land m has been shown earlier in chapter 5, that for a definite value of
I, m may have values 0, ± 1, ±2, ± 3 .... ± I i.e. (21 + 1) values for m are possible.
Conc~pts related to electronic spin, spin angular momentum and other related concepts are
taken in chapter 11.
1
Example 10.3 : <l>m = r:::= exp(im<l».Find out the eigen value taking this function with L z
. ,,21t
operator.
As
mh
Where L z value is m Ii or 21t
~l(l + 1) XII'
[See section 10.7]
1. Define angular momentum and show its relation with linear momentum. (See section 10.1)
2. Show that in quantum mechanical terms the components of angular momentum are
Lx =(~(y~z~)l
1 dz dy
Ly =(~(z~x~)l
dx
1 dy
and L. =(~(x~y~)l
dy 1dx
(See section 10.1)"
136 Quantum Mechanics  A Comprehensive Text for Chemistry
SYNOPSIS
Section Topics
11.1 Orbital and spinning motion of electron
11.2 Spin antisymmetry and Pauli's Exclusion Principle
11.3 Coupling of angular momentum vectors
11.4 Russell Saunder's Coupling (LS Coupling)
11.5 Relative Energies of terms and Hund's rule of Maximum Multiplicity
11.6 Spin Orbit coupling & Zeeman effect
11.7 Complex Zeeman effect (or Anonalous Zeeman effect)
In chapter 6 (Section 6.13), it has been introduced that Unlenbeck and Goldschmidt had
introduced that electron possess some intrinsic angular momentum of rotation which may be
expressed as momentum of electron due to its spinning motion around its own axis. In the previous
chapter, concepts related to angular momentum ofmoving electron have been introduced. Therefore,
in this chapter electron spin and its related topics are being introduced.
chapter 10. Similarly, S can also show commutation. The Eigen values for these two operators are
also similar. Similar to L2 and Lzoperator, S2 and Sz operators are there for spin angular momentum.
In order to characterise the Eigen function for both of them I, m/ and s, ms quantum numbers are
these.
As mentioned in chapter 10, for orbital angular momentum
... (11.2)
And
... (11.5)
And
... (11.6)
Similar to L for spinning motion of electron, on operating operators on the eigen function we
get
... (11.7)
And
... (11.10)
And
Electron Spin and Related Concepts 139
Similarly
... (11.11)
and
Sx. 5yand ~ also don't commute with each other similar to Lx' f.y and C operators. §2 and 5z
operators can commute with each other. This clearly shows that S vector and its one component
i.e. Sz can be ascertained similar to Land Lzvalues.
1 Ii 
~
Fig. 11.1 showing Sz vectors for a single electron
Considering intrinsic (or spin) angular momentum for electron, from Sand Sz operators this
may be concluded that
... (11.17)
where a. (s) and ~ (s) are Eigen functions for electronic spin. These functions are usually orthonormal
to each other which means that
f o.2ds == f ~2 ds == 1 }
and ... (11.18)
f o.~ds == f ~a.ds =0
For Heatom i.e. for two electron system total fo~r spin functions are possible which are given
in table 11.1
Table 11.1
Spin functions ms Sz
Symmetric o.(l) 0.(2) +~+~=1 Iii
Anyisymmetric o.(l) ~(2) +~~=O 0
Antisymmetric 0.(2) ~(1) ~+~=O 0
Table 11.2
Spin Functions
a(l) a(2)
~ (1) ~(2) 1
Now the question arises that out of these functions which is the correct function for Heatom
i.e. for 1S2 system? Answer of this question lies in one important principle known as Pauli's exclusion
principle. This principle is also known as Pauli's spin antisymmetry wave function principle.
According to this principle "for the systems where two or more electrons are there, total function
including the spin function should be anti symmetric i.e. this function should be anti symmetric
w.r.t. position of these two electrons". Therefore, on the basis of this principle the function.
will be valid function for the Heatom. This clearly indicates that in case of He  atom when two
electrons are in same orbital (e.g. 1S2), their spin motion (ms value) will be different i.e + ~ and 
Y2, while in excited state following spin function combinations are possible .
(1) Two angular momenta vectors 1. I & 1.2 can couple to have one resultant 1. vector whose
magnitude will be l(l+ 1) fi where I is quantum number. For 1. vector, allowed values for
I can be ascertained on the basis of the following series.
II + 12, II + 12  1 .................... (II /2) ... (11.22)
(2) Vector 1. can lie anywhere on the cone formed around zaxis and L z component will be
fixed while Lx and Ly components of the vector are not certain.
(3) 1.1 and 1.2 contributing to 1. vector are also of fixed magnitude as ~ll(ll + 1) fi and
~12(l2 + 1) fi,
(4) L z component of 1. vector will have length m, fi where m, will have 21 +1 values.
(5) In this way two options are left :
a. The values for 11 & 12 can be ascertained along with their z components m'l and m'2
even if I and m, are not certain. On the basis of this fact we can say that 1.1 and 1.2
have and 1. will not have a welldefined cones. This is not the position of coupling.
h. If I, 12 and I and m, are ascertained but m'l & m'2 are not certain. For example ml = II
and m'2 = 12 then m_l= mIl + ml = II +/2 ,this implies that 1. vector and its component
2
1.z are welldefined with welldefined cones. In such a case individually 1.1 and 1.2 will
also have welldefined cones, but their z components may not be certain. This is the
case of coupling.
In order to understand these facts let us consider an example.
Example 11.1 Let two particles have s = + lh and ms = ± Y2 . Explain their coupling.
Here II = sl = lh ; 12 = S2 = lh
mIl = m SI = ± Y2 and ml2 = mS2 = ± lh
may be obtained. In second step j vectors of each electron may couple further but in a weak manner,
this results in J angular momentum. This is known as jj coupling. In this scheme Land S are not
significant. LS coupling scheme can be explained on the basis of the following examples:
Example 11.2 : Consider 2 p 3 p electronic configuration where II = 1; 12 = 1; Sl = S2 = Yl.
Explain their L  S coupling.
In this case II and 12 can couple to give L = 2, 1, O. Similarly, S values will be 1,0 when L & S
will couple J = 3,2, 1, values will be obtained as shown below:
1,=1 tr L=2
~
12=1 L=1
r 8=1
S'=
~=1/2
1/2
1
5=0
L=2
S=1
tr J=3
L=21
5=1
/J=2
/
L=2
S=1
I
t J =1
In LS scheme energy levels are assigned symbols on the basis ofL value as per follows
L o 2 3 4
Symbol s P D F G
Multiplicity for these levels may be ascertained on the basis of the following rules:
( 1) If L ~ S. then multiplicity will be (2S+ 1) and which is known as spin multiplicity.
(2) If L :'S S then multiplicity will be (2L + 1) which is known as term mUltiplicity.
On the basis of Land S value, complete term symbols may be assigned to energy levels
(2S+I)X
which can be expressed as
,,
,  . 0
,, 1S 1So
,, "
,, ..................
,,, Singlet ,2
" '. ~::~::.~
States 
,, 10 '°2 • ~~1
,,,
"2
,,
: ,2
I ....... : ...    1
, ,.~ 0
: ,/ 3P2 ;:::::.:====~
: ""
,
: I·~'"
, Triplet \ '" ",,1
: " States \ '" :.~'o
,
: I
" \\ 3p, "",1
, I \
, I \
, I \
, I \
,
:
,
,
,
I
I
I "
I \
'._ 0
, I
:t': "
~:'
t'
p2
Fig. 11.3
146 Quantum Mechanics  A Comprehensive Text for Chemistry
Example 11.4 : Find out term for d2 system and draw their energy level diagram.
In case of d2 system, L values will be 4, 3,2, 1, 0 and terms for this system will be G, F, P, D, &
S. In this system, S will have the value 1 and 0 which shows that terms may be triplet or singlet
terms. Taking into accounts only equivalent electrons, the valid terms will be IS, 3p, I D, 3F and IG
Their energy level diagram with microstates is shown as per following figure 11.4.
,,
,
'S

'So
0
,
,,
,
,:rsingIetcr~,:
'G
"
'G.
~4to4
: States '
,, ' '
,: '.=  ~ 2 to2
, '0 '02
,,, ~2 to2
, ~~
3P2
:
:
~.~.~t~
3p
~
"' ...
"' ...
3p,
E::::: 1 to1
: ,r    . . , ,
"",.""",,,
3po
0
f ! Triplet "" ~
~ 4 to4
3F.
:
,, ,,
: States '"
~
~
~
,: ,:
,,
,,, ,,,
,, ,,
,,,,,,
"
"
"
""
"
""
:",""
2
d
Fig. 11.4
iA
Gauss's law ~m=C
SI ~m =iA
} ... (11.27)
Electron Spin and Related Concepts 147
II
t"m
= (~)
21tr
(1tr2) ~ = ~
c 2c 1
and S.1. : J.lm =
vre
2 j ... (11.30)
Ilm
Flg.11.5
148 Quantum Mechanics  A Comprehensive Text for Chemistry
Or m = ~l (l + 1) cos <l>
~ L
~m ,..
~m~~~~L "2
~m :..( ______________ . L
Fig. 11.6
Electron Spin and Related Concepts 149
In the presence of magnetic field these magnetic moment vectors show precession with magnetic
field. Because of quantum restriction these vectors can't align with magnetic field. Let us suppose
that in B magnetic field an electron possess the potential energy V. These two parameters can be
correlated to each other as
V =BJ.1z ... (11.39)
= V =B (J.1m Cos <p) ... (11.40)
E (m = + 1) = En + BIlB
E(m=O)=E n
1
... (11.45)
E(m = 1) = En  BIlB
Therefore, in the presence of external magnetic field energy levels of porbitals may get split
as a result of which in the presence of magnetic field spectral lines for the cases in which porbitals
are involved may also get split. This effect is known as Zeeman effect. Fig. 11.7 shows such splitting.
2p
r 
. m:::0
+   
 m:::1
1s _ _l_ _ _                       _.
It It
1S
150 Quantum Mechanics  A Comprehensive Text for Chemistry
Fig. 11.7
S = ~s(s+l) ;,
For electron ms will have s, (sl) .......... (sl) allowed values. For a single electron
S =~and
h
S = ~Yi(Yi + 1) 21t ... (11.49)
or ... (11.53)
Electron Spin and Related Concepts 151
Therefore, taking spin only formula magnetic moment for electron will be
Therefore, for electron total energy incorporating L & S angular momenta will be
E =En+BIlBm+2B IlBms ... (11.59)
For s orbital m = 0
= E = En + 2BIlB ms ... (11.60)
... (11.61)
Similarly for porbital
m= 1 ms =~ E =E n +2BIlB
ms =~ E =E n
m=O ms =~ E = En + BIlB ... (11.62)
ms =~ E =EnBIlB
m=l ms =~ E =E n
ms =~ E = E n 2Blls
Considering energy levels mentioned in equation 11.61 and 11.62 following energy level diagram
may be drawn on the basis of which this may be concluded that in presence of external magnetic
field due to L & S coupling effect, Atomic spectral lines may split.
152 Quantum Mechanics  A Comprehensive Text for Chemistry
+1/2
,
, ,,
, ,, ,
+1/2
, ,, ,,
,
~~~·m='1"""'
,
... "..,.., ,, +1/2
2P==~==
.::...:: .J
~_ m=O
~ "
~........:: .......1/2
'
~ ~    .,.:+4
~_ 112
m=1
1/2
"""
",'"
1S _ _...L_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ...:._.!.._!.

",'
,'"
1s ~~
~~
~~
~~
If
SYNOPSIS
Section Topics
12.1 Symmetry elements and their related symmetry operations
12.2 Matrix representations for symmetry elements
12.3 Symmetry groups and point groups
12.4 Representation of a group
12.5 Character Table
12.6 Reducible and Irreducible Representations
12.7 Great Orthogonality Theorem
12.8 Reduction formula and its use
12.9 Projection operator and its use construction of SALC's (Symmetry adapted
linear combinations).
Symmetry has a significant role in the determination of crystal structures and spectroscopic
properties viz. Infrared and electronic spectroscopic properties ofthe molecules. Quantum mechanics
provides a basis for solution of molecular structure. Therefore, consideration of symmetry of the
molecule is basically its consideration in quantum mechanics. Therefore, it is required to have
mathematics which provides a bridge between symmetry, properties of molecule and quantum
mechanics and such mathematics is g.1')Up theory. This chapter includes introduction to symmetry,
properties of molecules viz. symmetry elements and related symmetry operations, their
representations, point groups and their character tables, great orthogonality theorem, reduction
formula with its applications, direct product representation and symmetry adapted linear
combinations taking suitable example.
155
156 Quantum Mechanics  A Comprehensive Text for Chemistry
Identity E
Inversion centre Inversion through this point (centre)
Axis of Symmetry Cn Rotation through this axis by an angle 8 (8 = 360 0 /n) where n is the
order of the axis.
Plane of symmetry a Reflection through this plane
Improper axis of rotation Sn Rotation through this axis by an angle 8(8=360 0 /n) (where n is the
order of the axis) followed by reflection through a plane
perpendicular to this axis.
Some of the example's showing symmetry elements and their related symmetry operations
are given below:
Identity (E): Identity means doing nothing to the molecule. Therefore, a well defined
configuration of the molecule is its identity for example :
Fig.~2.1
Concepts of Symmetry and Quantum Mechanics 157
In above examples position of atoms have been fixed by numbers viz. 1, 2, 3   and no
operation is being carried out on them. Therefore, these configurations may be treated as their
identities.
Inversion Centre (i) : It is an imaginary centre which may be present inside the molecular
body (on atom or in space) through which if inversion is carried out would yield a similar a equivalent
structure. For example:
" li
Cl l H2
/'
CltC~
H:' CI,
Fig. 12.2
F2 Fl
" BF Cl3
~ " BF2 C23
~
/ 3 /
Fl F3
F3 F2
" C3 "
~
F; BF
1
3
F; ® BF
3
/N
~ H3
Hl
\"H2l C~
( 1"H3
H2 ®
C 2 H2Cl 2 (cis) and C 2 H 2 Cl 2 (trans) possess C 2 axis but their existence are different. In
CisC 2H2CI2, C 2 is parallel to the molecular plane but in transC2H 2CI2 , C2 is perpendicular to the
molecular plane.
Hl H2 H2 Hl Hl H
\C / Cl2 \ C =C / C22 \ /2
l
=C 2 ~
2 l ~ Cl =C2
Cl l
/ \ CI
CI
/ \ Cl CI,
/ \ CI
2 2 l 2
and
H2 CI, Hl CI2 H2 Cl l
\C / Cl2 \ C,=C / C22 \C /
2 =C, ~
2 ~
2=C l
/ \ / \. / \
CI 2 H, Cl l H2 CI2 ® H2
Concepts of Symmetry and Quantum Mechanics 159
BF3 certains 30v 's and one 0 h (i.e. molecular plane itself). Position of3o/s are shown below:
NH3 contains 30v 's and their existence can be made clear according to the following figure
160 Quantum Mechanics  A Comprehensive Text for Chemistry
,,
,,
, ,,
,,
,
In case of Cis  C 2 H2 CI 2 two cry's are there out of which existence of one is shown in the
following figure and other in the plane of molecular plane.
cr V2
In case of trans  C2H 2Cl2 one crh is these which exists in the molecule as molecular plane.
XeF 4' AB4 type square planer molecule contains one crh (the molecular plane) 2cry's and 2crd 's
whose existence can be made clear according to the following figure.
"F F/
'~ /'
Xe
/~
~F' F,
cr,' ~,
Concepts of Symmetry and Quantum Mechanics 161
Improper Axis of Symmetry (So) : It is defined as an imaginary line which passes through the
molecular body through atom or through space on or along which if rotation by an angle 8 (8 =
360 0 /n) in clockwise direction is carried out followed by reflection through the plane perpendicular
to this axis would yield the similar or equivalent structure. S6 axis is present in staggered ethane
which passes through central CC axis. S3 axis is present in PCls molecule
H, 1
3 ',,f,
, '2
\I
5
Cia,
~:
~~"'Cle,
Cla2
ill
'S3
If order of So is odd (Le. n = odd) it requires 2n operations to reach upto identity as shown
below (Taking example of 53 axis).
5~ = C~ .a1 = S~
S; = C~ .a2 = C~. E= C~
S; = C~ cr3 = E.cr =a
S~ = C~ at = C~. E = C~
S~ = C~ as = C~. a = S~
S~ = C~ . a 6 = E . E = E
Similarly, it requires n operations to reach identity, ifn = even in case of So axis. This is shown
below (taking example ofS 6 axis)
S~ = C~. a1 = S~
52
6
=C 62 cr2 = E = C62
162 Quantum Mechanics  A Comprehensive Text for Chemistry
s~ = C~ . a5 = C~ . a = S~
S:=C~. a6 =E. E = E
E= 0
1 01 OJ0
(001
Reflections: Considering x, y. z reference frame of axis i.e. considering a xy a yz and axz ,matrices
for plane of symmetry may be written as
0 oj
ayz = ( I0
~)
1
O. 0
~ (~
~J
0
au 1
0 0
~ (~ ~J
0
aw
0
Inversion centre (i) : Considering x, y, z reference frame of axis matrix representation for
inversion centre is given by
OJ
()
1
Proper axis of rotation (en>: For rotation axis or proper axis of rotation i.e .. for Cn axis with
an assumption that zaxis may be considered as proper axis of rotation the matrix w.r.t. Ji., y. z
coordinate is
Concepts of Symmetry and Quantum Mechanics 163
sinS
cose
o
Or matrix for Sn is
cose sine 0]
Sn = sine cosS 0
[
o 0 1
COS180. sin180·
Matrix for C 2 = sin~ 80· cos180·
(
o
(e = 1800 in case of C 2 axis)
1
Matrix of C 2 = ~
(
C, matrix ~ "~l
( ~ F;{
Yz
0
0
0
164 Quantum Mechanics  A Comprehensive Text for Chemistry
No LINEAR OF
HIGHSYMM
PROPER AXIS
Cn?
Yes
Yes ONE
a?
No Sn COLINEAR
WITH Cn ? No
Yes i?
No
n EVEN?
Yes
OTHER
SYMM
EXCEPT
No
No
Yes Y,:s ~
ad?~
Fig. 12.3
166 Quantum Mechanics  A Comprehensive Text for Chemistry
BF3 : It is not a linear molecule or a molecule with high symmetry. It is the molecule with axial
symmetry and it possess C 3 axis as principal axis with perpendicular 3 C 2 axes. Apart from it, it also
contains 3 av's ilnd ah • Therefore, its point group is D3h
Trans C 2H 2CI 2 : It is not a linear molecule or a molecule with high symmetry. It is the.
molecule with axial symmetry and it possess C2 axis which is perpendicular to the plane of molecule.
Apart from it also contains inversion centre 'i' and a plane a h• Therefore, its point group is C 2h
CisC 2H 2C1 2 : It is not a linear molecule or with high symmetry. !t is the molecule with axial
symmetry and it possess C 2 axis which is present parallel passes through midpoint ofC = C. It also
contains 2 a'v. Therefore, its point group is C 2v
p.
Concepts of Symmetry and Quantum Mechanics 167
R,
Ry
.YI'+y
1 1 pz
1 1 1 Rz
1 1 1 Px' Ry
I I pyRx
Considering d{)rbitals as function space complete table is as follows:
C 2v E C2 0:,= O:y::
't2 1 1 ~ xy
't3 1 1 PxRy xz
't4 I I Py Rx yz
In the table mentioned above 't\ 't 2 't3 & 't4 are representations ofC 2v point group. This type of
table is known as character table.
~
o OJ
010
o 0 1
~~1 ~J
l~ ~+1
Character = 3 Character = 1
axz
l~ ~ ~J
Character = 1 Character = 1
Concepts of Symmetry and Quantum Mechanics 169
C,v
Tx,y,z
I:
Therefore the commulative representation may be represented as
~: G
n
G~ x,y, z
all
classes
C 2v E C2 C;xz C;yz
A] 1 1 Pz
A2 1 1 Rz
B] 1 1 Px Ry
B2 1 1 Py Rx
r"yz 3 1 xyz
(iii) Sum of squares of characters in any irreducible representation must be equal to order of
the group, this can be shown as follows:
A}=12+F+12+12=4=h (i.e. order)
A2 = 12 + 12 + (If + (_1)2 = 4 = h (i.e. order)
H} = 12 + (1)2 + 12 +(_1)2 = 4 = h (Le. order)
H2 = 12 + (1)2 + (1)2 + 12 = 4 = h (Le. order)
(iv) Two different irreducible representations i.e. either A) A2 B) or B2 are orthogonal to each
other. This can be proved by taking example of A) & A2
1 x 1 x I + 1 xl xl + 1 x 1 x(I)+ 1 xl x(I)=O
(v) It is obvious that in all the irreducible representation i.e. A} A2 B} & B2 characters of the
matrices belonging to the operations of the same class are identical i.e. characters of the
matrices belonging to E, C 2 O'xz or O'yz are identical.
This proves the G.O.T. for C2v point group.
Where aJ :::: no. of times that an irreducible representation with characters XJ(R) appears in the
reducible representation with characters X(R) and nr is the number of operations in a class.
Example 12.5 : Reduce the reducible representation r xyz for C 2v point group
Please refer to character table for C2v point group and applying reduction formula for r xyz and
considering A}, A2 H) & B2 representations.
aA } = 4"1 [lxlx3+1XIX(I)+IXIX1+1Xlxl] =)
AI pz
A2 1 1 Rz
BI 1 1 1 PxRy
B2 1 1 1 PyRx
y~
Hl H2
Therefore, two SALC's for H 20 molecule are qJ 1 + qJ2 & qJ 1  qJ2 which on normalization
becomes
SYNOPSIS
Section Topics
13.1 LCAO  MO treatment for H 2+ ion
13.2 LCAO  MO theory for H2 molecule
13.3 Huckel  molecular orbital theory
13.4 Valance bond theory
13.5 Concept of hybridization
Concepts & theories of chemical bonding can be understood in a better way in the light of quantum
mechanics. Linear combination of atomic orhitals, i.e., LCAO and formation of molecular orbital,
i.e., LCAO  MO concept, valance bond concept as \Yell concept of hybridization can be understood
in a better manner in the light of qual1tum mechanics. In this chapter these concepts are included in
detail.
174
Theories of Chemical Bonding 175
e,
~~~HB
Fig. 13.1
... (13.1)
The electrons in this case will try to occupy the lowest bonding M.O. with opposite signs. The
total molecular wave function will be written as
'f' tot = 'f' spa('~
'f' Spin ... (13.2)
Where
'f' = 'f' (I) '¥ (2) ... (13.3)
space ,. +
... (13.5)
C I C

 I
2  V ~(I SAB)
... (13.7)
and the energy of the system can be determined by applying variation thereon as
176 Quantum Mechanics  A Comprehensive Text for Chemistry
... (13.8)
On solution, the minimum energy for the system comes to be  30.68eV (2.96 KJ molI) at
the stable internuclear distance, i.e., 73 pm. The bond energy ofH2 molecule is larger than that of
H2"  ion and the bond distance is smaller than that of H2+ion.
In order to understand M.O. theory for 7t electron system HMO theory was proposed. This
theory is given in section 13.3.
Fig. 13.2
'¥ for the allyl system may be written as
'¥ = c\ <1>\ + c2 <1>2 + c3 <1>3 ... (13.15)
As in allyl system each and every Catom is Sp2 hydrized with <1>1,<1>2 and <1>3 as wave functions
for 1,2 and 3 Catoms respectively. Secular determinant for this system may be written as
HII  ES II HI2  ES I2 HI3  ES t3 1
H21  ES 21 H22  ES 22 H 23  ES 23 i = 0
H31  ES 31 H32  ES 32 H33  ES 33 ... (13.16)
Theories of Chemical Bonding 177
aE ~ o
~ aE ~ =0 ... (13.17)
o ~ aE
Dividing the determinant by ~
(a E)/~ 1 o
1 (aE)/~ 1 =0 ... (13.18)
o 1 (aE)/~
x 1 o
x 1 = 0 ... (13.19)
o 1 x
Solution of above detenninant yields x = 0, ± ...J2. Therefore, three energy levels for xelectrons
of allyl system may be obtained
EI =a+...J2 ~
E2=a+O~
a"h~
_....:.t__ a
_t.!"J,:.. a + ...J2 ~
Fig. 13.3
178 Quantum Mechanics  A Comprehensive Text for Chemistry
Putting x = J2
... (13.21)
Similarly corresponding to x = 0
QI = Ln c."J
I I
... (13.25)
Where CJ1 is the probability of finding electrons in jlh level and nj is the number of filled electrons
in the level. Therefore for allyl radical charge densities for the three levels will be
ql =2X(±)+IX(~)=1
q2=2(~)+lX(O)=1 and
q3 = 2 x (±) + x (~)
1 =1
Bond order: Similarly charge density between two atoms i and k is bond order which may be
calculated as
all levels
L nj C ji C jk ... (13.26)
j=1
where CJI and CJk are coefficient for ith and kth atoms and nJ is the no. of electrons filled in levels.
Applications of HMO theory :
Butadiene system: For this system secular determinant may be written as
Theories of Chemical Bonding 179
x I 0 0
1 x I 0
=0
oI x 1
001 x
cccc
Fig. 13.4
On solution of above determinant x will have values ± 0.718 or ± 1.718. Therefore, energy
levels for butadiene are
E( = a+ l.718 p
E2 = a + 0.718 P
E3 = a 0.718 p
E4 = a1.718 p ... (13.27)
MO diagram for this molecule is shown below
a1.718 p
a0.718 p
iJ,
a+0.718p
iJ,
a+ l.718 p
Fig, 13.5
Energy for this system will be 4 a + 4.472 p
Ethylene system :
This system may be represented as
cc
Fig 13.6
Secular determinant for this system may be written as
\ ~ ~ \ =0 .. (13.28)
On solving it x = ± 1 and two energy levels may be obtained for the system
180 Quantum Mechanics  A Comprehensive Text for Chemistry
u ~
u+~
Fig. 13.7
Therefore for ethylene molecule, energy will be
E =2u+ 2~ ... (13.30)
Considering butadiene as combination of two ethylene molecules, energy of butadiene maybe
calculated as
E = 2 (2 u + 2~) = 4 u + 4~ ...(13.31 )
As per calculation shown previously energy for butadiene is 4 u + 4.472 ~
=.1.E = (4 + 4.472 ~)  (4u + 4~)
.1. E = 0.472 ~ ... (13.32)
This energy (.1.E) may be the stabilization energy for butadiene due to conjugation.
]n case of ethylene two M.O.'s will be
... (13.33)
1
As
2
Cyclobutadiene system:
For cycIobutadiene system secular determinant may be written as
Fig, 13.8
Theories of Chemical Bonding 181
x 1 0
1 x 1 0
o x 1 =0 (13.35)
lOx
On solving this E may be obtained as 4 a + 4~ (for four electrons). If this system would have
been considered as combination of two ethylene molecules then also its energy will be E = 4 a +
4~. Therefore stabilization energy for cylobutadiene will be
Fig. 13.9
For this system secular determinant may be written as
x 1
1 x = 0 ... (13.37)
1 1 x
On solving this determinant values for x will be 2, 1 and 1 and the corresponding energy levels
will be
E) =a+2~
A
E2 =E3 =a )J
and
Therefore energy level diagram for cyclopropenyl cation, radical and anion are as follows :
a~ i
a+2~
Fig. 13.10
Energy for cation will be
E =2 a+4~
And its stabilization energy will be 2~. Energy for radical will be
E = 3 a + 3 ~ with stabilization energy ~ and for anion energy will be
182 Quantum Mechanics  A Comprehensive Text for Chemistry
E = 4 a + 4~ with stabilization energy as zero. 1t wave functions for this system will be
In case of symmetric interaction, electronic waves are in same phase in between the nuclei, i.e.,
the spin of two interacting electrons are opposite or this results in the lower energy state than the
isolated HA & HB atoms. If this type of interaction is there covalent bond forms between HA and HB
with the corresponding energy
... (13.45)
This energy of the system has been attained at stable bond distance of H2 molecule (i.e., rs =
087 A0). In case of antisymmetric interaction of orbitals as explained by 'I' AS; spin of two combining
electrons are parallel, i.e., the two electronic waves results in the formation of state of higher
energy. This is given by
... (13.46)
E AS will be the higher energy state than corresponding interacting atoms because of this
anti symmetric combination formation of molecule can't take place. Pauling & Slater suggested
two more ionic structures which can contribute to the formation of H2 molecule.
According the modification suggested by them during symmetric interaction 'l's will be
'l's = 'l'cov + A. 'I'.onic, ... (13.47)
Where A. is the degree of ionic character in the bond which is 0.17 for H2 molecule and
'I'.omc = '1'111 + 'l'tV ... ( 13 .48)
Where
'l'IIl = 'I' A 1 'I' A2 ... (13.49)
and 'l'tV = 'I'B1 'I'B2 ... (13.50)
By this modification rs' i.e., bond distance for symmetric combination for H2 molecule was
calculated as 0.86 A 0,
The features or significant points regarding valance bond theory are:
(i) All atomic orbitals retain their identity during formation of valance bond but only valance
electrons lose it
(ii) During bond formation only valance electrons remain effected.
(iii) Each and every atom involve in the valance bond formation require some energy to have
unpaired electron for the formation of bond.
(iv) Strength of bond formed depends upon the extent of overlapping. So, if the overlap
integral S > 0 stable bond will be formed, if it is S < 0 no bond will be formed and if S =
othere is neither attraction nor repUlsion.
184 Quantum Mechanics  A Comprehensive Text for Chemistry
(v) If there is symmetrical interaction, i.e., 'I's m.o. formation is there between interacting
atomic orbitals, a molecular orbital (amo ) is formed. This happens in case of ss or Pz  Pz
bond formation.
(vi) If interaction is less i.e. in case of sideways overlapping between Px  Px or Py  Py a.o's
1t bond is formed.
(vii) Extent of overlapping is more in case of a bond instead of 1t Bond.
(viii) Rotation around a bond is possible and
(ix) Isomerism can be shown along a bond formed
Different types of AO's interaction and formation of a and 1t bond is shown in figure 13.11
+
0 •• bond
+ cP .
+ ~
ITpxPx bond
Fig. 13.11
has been introduced known as hybridization which involves the formation of hybrid orbitals. Here
hybridization has been explained taking examples of Carbon atom. As mentioned above with
electronic configuration 1S2 2s2 2px I 2py I, carbon should be taken as bivalent atom with two unpaired
or uncoupled electrons with valance angle of about 90°. But it has been observed that in most of the
stable organic compounds carbon is in tetravalent state with four unpaired electrons and its electronic
configuration in excited state is
Is2 2s 1 2Px l 2p yl 2 PZ l
If it is assumed here that all the four orbitals. viz. 2s and 2px 2py & 2pz are involved in bond
formation, then the four bonds formed by carbon atom will be of different kinds on 3 bonds with
porbitals will be of different nature is compared to 1 bond with s orbital as overlapping properties
of s an~ p orbitals are different. But if we see the case of CH 4 and other carbon compounds it has
been observed that all the four bonds of Carbon atoms are of same nature, i.e., identical bonds are
formed by the carbon atom with equivalent energy at equal angles viz., 109°28' to each other to set
up in regular tetrahedron geometry. This can be understood on the basis of hybridization. Some
points or features regarding hybridization are as follows:
(i) Hybridization is not a real physical phenomenon but it is a concept to explain the
geometries or shapes of different molecules.
(ii) AO's of central atom which have equal or comparable energies can undergo hybridization
to give hybridized A.O's.
(iii) No. of A.O's undergoing hybridization should be equal to no. of hybrid AO's formed as
it is a phenomenon of intermixing of AO's of equal or nearly equal energy.
(iv) Energy of hybrid A.O's formed should be equal.
(v) Hybrid A.O's formed in Central atom should be mutually orthogonal and normalized set
of A.O's, i.e., orthonormal sets of hybridized A.O's are formed after hybridization.
(vi) These hy.. bridized A.O's of central atom arrange themselves in space in such a way that
they are far apart from each other as a result of which shape is attained by the molecule.
Carbon may have Sp3, Sp2 and sp hybridization in its compounds. Construction of hybrid orbitals
and angle between the hybrid A.O. 's can be explained as per follows:
Sp3 hybridization :
Formation of sp3 hybrid AO's can be shown as per figure 13.12.
Sp3 hybridization
These Sp3 hybrid A.O's are formed by the linear combinations of one 2s and three 2p orbitals of
carbon atom. The wave functions offour equivalent hybrid orbitals obtained may be represented as
'¥I =al'¥s+bl'¥px+cl'¥py+dl'¥pz
'¥2 = ~ '¥s + b2'¥px + c2'¥py + d2'¥pz
'¥3 = a3'¥s+ b3'¥px + c3'¥PY + d3'¥pz
And '¥4 = a4 '¥s + b4'¥px + c4'¥PY + d4'¥pz
Where a p a2 a3, a4 , b p b2, b3, b4 , c p c2' c3' c4 ' d p d2, d3 and d4 are mixing coefficients of A.O's
which are involved in Sp3 hybridization. As these hybrid orbitals are completely equivalent. Their
scharacter must be same. This implies that
aI 2 = Y4 or a I = Yz
Similar equations can be written for all the hybrid orbitals
a 2 =a 2 =a 2 =a 2 =Y4
I 2 3 4
~a I =a_=a
;, 3 =a4 =Yz
Let us assume the direction of first hybrid orbital along xaxis only. Therefore in '¥ I ' '¥2PY and
'¥2pz will be zero i.e. these will not have any contribution in '¥I this implies that c i = 0 and d l = 0
Since '¥I should be normalized
~aI2+bI2= 1
Or b I 2 = la2 = 1  Y4 = %
or b =
I
Ji
2
As '¥ I' '¥2' '¥ I '¥3' etc. should be mutually orthogonal to each other
Therefore
a l a2 + b l b2 =0
a l a3 + b l b3 = 0
a l a4 + b l b4 = 0
from above equations this may be concluded that
1 1
 x
2 2 1
Ji/2 = 2)3
and
Theories of Chemical Bonding 187
As qt2 lies in xz plane. therefore contribution of Py in qt2 is zero. Hence we may write
c2 =0
As qt 2 is itself of normalized
Therefore al + bl + dl =1
=> dl = 1 (~ + bl)2
= 1(a/ +b/)
=1(±+/2)=~
d
2
=
'1fi3
Considering orthogonality of qt2' qt 3 and qt4 wave functions
a2a3 + b 2b 3 + d 2d 3 = 0
~a4 + b2b4 + d 2d 4 = 0
which implies that
and
1 1
+ 1
 4Jd2 = .j6
=>C32 =Y2
Or C3 = + "liz
Similarly
a/ + b/ + c/ + d/ = 1
188 Quantum Mechanics  A Comprehensive Text for Chemistry
1 1
~C2=~C=
4 2 4 ~
c3 and c4 can't be same. Therefore to make '1'3 different from '1'4 root c4 should be negative, i.e., c4
= ve or C4 = "Yz
Incorporation of all the coefficients '1'1' '1'2' '1'3' and '1'4' may be written as
1 J3
'I' ='1'+'1'
1 2 s 2 P"
~
'I'
3 pz
1 1 1 1
'1'3 ="2 '¥s 2J3 '¥px+ ~ '¥py .J6'¥pz
1 1 1 1
and '1'4 = "2'¥s 2J3 '¥px ~ '¥py .J6 '¥pz
Where a is angle ofa position vector with zaxis and <I> is angle ofprojection of the vector on xy
plane with xaxis.
Incorporating '¥s' 'I' px' 'I' py and'll pz' hybrid orbitals '1'1' '1'2' '1'3 and '1'4 may be written as
'1'3 = i  2~ (J3 sin a cos <1» + ~ (J3 sin asin ~ )  ~ (J3 cos a)
'1'4 = i  2~ (J3 sinO cos <I»i (J3 sin Osin <I> )  ~ (J3cosO)
It was considered earlier that '1'2 is in xz plane therefore <I> must be 180°. So, putting value of
<I> = 180°.
Theories of Chemical Bonding 189
1
=> "2 cos a  J2 sin a =0
1
tan a = 2J2 = 0.354
e = 19°28'
Where e is an angle between zaxis and the axis of wave function 'P 2 • Therefore angle between
'1'1 and 'P2 will be 90° + 19°28' = 109°28' (as'll I is considered along x axis). Similarly all other
angles can also be calculated as 109°28'. This shows that Sp3 hybrid orbitals attain a regular
tetrahedron geometry with angle 109°28' as shown below:
Sp2 hybridization: In this hybridization Pz orbitals do not take part or participate. Therefore,
sand Px' Py orbitals are involved in hybridization which results in the formation of three hybrid
AO's, viz., 'II) 'P2 & 'P3
'PI = a l 'Ps + b l 'I'px + C) 'Ppy
'1'2 = a 2 'Ps + b2 'I' px + C 2 'P py
'1'3 = a 3 'Ps + b 3 'I'px + C 3 'I'py
Where a's, b's and c's are mixing coefficients of AO's used in these hybrid orbitals. As all the
hybrid orbitals are equivalent therefore each of it must have same s character.
=> a ) 2 = a_
I.
2 = a 2 = 113
3
190 Quantum Mechanics  A Comprehensive Text for Chemistry
1
Or a l = a 2 = a3 = .J3
Let us assume qt 1 is along x  axis
=> c1 = 0
As qt 1 is a normalized orbital
Or (~J +b~ =1
b
1
fI
= V3
As qt 1 qt2 and qt 1 qt 3 are orthogonal to each other
=> al~+blb2 =0
And
And
1 1
x
.J3 .J3
~%
As qt 2 and qt 3 are normalized itself
=>a22 +b 22 +c22 =1
Or c/=1(~2+b/)
Theories of Chemical Bonding 191
I
c3 =± .J2
Since C2 and C3must have different signs therefore if c2 is positive c3must be negative. Therefore
hybrid orbitals '1'1 '1'2 and '1'3 in this case are
I 1 1
'I' =  ' I '  'I' +'1'
2 .fj s J6 px .J2 py
I 1 1
'1'3 = .fj '¥s J6 'I' px  .J2 'I'py
Calculation of bond angle and shape
In order to calculate the bond angle between Sp2 hybrid orbitals, Let us take into account '¥s 'I'px
and 'I'py in terms of polar coordinates.
'¥s =I
'I'px = .fj sin 6 cos <I> and
'I'py = .fj sin 6 sin <I>
Therefore
And
d'¥2 1 {3
d<l> =.J2 sin <I> + ~r2 cos <I> =0
192 Quantum Mechanics  A Comprehensive Text for Chemistry
+. +
Sp2 hybridization
Fig. 13.14
sp  bybridization : This hybridization is also known as diagonal hybridization. In this
hybridization only one sorbital and one p orbital (i.e. Pz) intermixes to give sp hybridized A.O's
wave functions for sp hybridized A.O's i.e. '1') and '1'2 may be written as
and
where a's and b's are mixing coefficients As both the hybrid AO's are equivalent. Therefore both of
them contain equal s character and p character
~a2=a2=Y2
) 2
Or
As '1') is normalized
~
Theories of Chemical Bonding 193
1
=> 1 
2
=> b =_1_
1.[2
As 'II I 'II I are orthogonal to each other
= a l a2 + b l b2 = 0
=>
And
Bond angle between the hybrid A.O's 'III and '112 can be calculated by considering polar
coordinates
'IIs = 1
'IIJXZ = .J3 cos e
On substituting 'lis and'll pz
>~ ~ sp hybridization .
Fig.13.15
~
194 Quantum Mechanics  A Comprehensive Text for Chemistry
SYNOPSIS
Section Topics
14.1 A brief account of Hartree Fock self consistent field theory
14.2 Koopman's Theorem
14,3 Introduction to Quantum Chemical Packages
14.4 Applications of Quantum Chemical Softwares
Use of computer for calculations in Quantum chemistry had started since 1960's. Since then
use of computer softwares and development of packages began for the quantum chemical
calculations. With the advancements in technology and upgradation in hardware techniques, software
packages have also improved with all generations of computers. These softwares or packages form
a basis of calculations of physical properties of the molecular systems under study. These packages
have been improved time to time depending upon the needs for the calculations of the parameters
for molecular systems. Softwares or packages which are in use nowadays come under either
abinitio or semi  empiricial categories of packages. These softwares or packages are ~,ased on
Hartree Fock self consistent field theory. In this chapter introduction to (i) Hartree Fock self consistent
field theory (HFSCF), (ii) Abinitio and semi  empirical packages and (iii) some applications of
computer softwares or packages in theoretica1 or quantum chemical calculations are included
197
198 Quantum Mechanics  A Comprehensive Text for Chemistry
For such a system showing appropriate Hamiltonian, energy of the system may be given by the
equation
... (14.2)
As ell's are normalized so, 'II may be also considered as normalized wave function Hamiltonian
Or ...{14.4)
Or ...{14.7)
In above Hamiltonian VI'S are potential terms which can be expressed as follows for 02
electrons system
qlq2
V12 = rl2 ... (14.8)
Or V12 =
J(e)(e)leIliI 2
<tt2
... (14.9)
rl2
... (14.10)
In the method proposed by Hartree repeated interactions have been applied to the system to get
self consistent value for interaction term within the specified potential field. For this purpose trial
Introduction to use of Computers in Quantum Mechanics 199
functions <I>'s are chosen and applied in their respective Schrodinger equations as
... (14.11)
• <1>' can be obtained from equation 14.11 similar, equations can be employed for <1>2 <1>3 and so on
within the same specified potential field to get self consistent value. Therefore, this theory is known
as self consistent field theory. Probability density can be obtained commulatively from <1>1 <1>'2'
........ as
... (14.12)
And the total wave function for the system may be obtained as
\}I = <1>'" <1>'2 <I>'r ............ <1>'0 ... (14.13)
Energy can be computed as
... (14.14)
Where J = average coloumbic energy which counts for average repulsion between I and j
atomic enter~ in the system.
Hartree calculate energy and ionization potential values for various atoms, molecules and ions.
Energy of some atoms do not match well with the exact value
Hartree Fock Self Consistent Field Theory (HFSCF)
Fock modified the theory proposed by Hartree & Fock used antisymmeterized wave function as
1
\}I = vIn: <I> 1(I) '1'1 ",(2)
••••••
'" (2)
'I':Yz ... (14.15)
ni
In above \}I's equation <1>1(1) <1>1(2) together show a complete set of spin orbital for electron 1.
Combination of such similar sets of spin orbitals constitute '¥ Fock applied Fock operator which
also includes electron exchange terms, with Fock operator equation may be written as
F<I>I = EI <1>1 ... (14.16)
In terms of (a.u.) atomic units Fock operator may be expressed as
n/2
A Z","A A
F =  Y2 v~
1
 r + LI (2J i  k j)
j=1
... (14.17)
i
Where J operator is coloumb operator and K (i) is exchange operator. Choosing any arbitrary
function of operation of Kj ' (1) may be shown as
First term of the Fock operator may be treated as kinetic energy and second term as potential
energy term for one electron numbers as (1) Collectively, with this modification, the self consistent
field theory is known as Hartree Fock self consistent field Theory (HFSCF)
200 Quantum Mechanics  A Comprehensive Text for Chemistry
Roothanian Proposal :
The key development that makes feasible the calculation of accurate SCF wave function was
Roothanan's proposal to expand the spatial orbitals <1>1 as linear combinations of set of one electron
basis functions xs :
... (14.19}
To exactly represent MO's for a molecular system <l>j is the basis offunctions. In practice finite
number of basis sets of functions are used. If b is large enough and functions XI are well chosen
M.O. 's for the molecular system can be represented with negligible error. With Roothanian's proposal
Hartree Fock equation may be modified as
Br NH2
01
0 2
+
0 3
CI CI CI
& 6
4
.& CI
5
~
. & 6
NH2
Fig. 14.1
160
Reaction Coordinate •
Fig. 14.2
These values shown in the above diagram are AM 1 computed values using MOPAC package.
Similar studies are also available in literature.
(8) Theoretical studies of electronic and geometric structures of the compounds
Theoretical studies of electronic and geometric structures of compounds can be done successfully
using these packages. Some of such studies are carried out on organic compounds which are used
as ligands in the formations of metal complexes. Such studies were carried out on Schiff base
ligands some of them are shown below:
Introduction to use of Computers in Quantum Mechanics 203
(3)
Fig. 14.3.
Such studies shows that electron densities in Schiff bases are ample and maximum on
azomethinic nitrogen. This fact supports that these Schiff bases can coordinate to central metal
atom through azomethinic nitrogen.
(C) Computer simulation of IR spectra using these packages:
Normal modes analysis of some ofthe compounds can also be performed using specific keywords
with the help ofthese computer packages. On the basis of normal mode analysis computer simulation
of IR spectra can be done. One such study for SBenzyl 1~M(2furyl methyl ketone) dithio
carbazate schiff base has been carried out with AMI, PM3 MNDO and MNDOd methods. These
computer simulated IR spectra are shown in figure below.
1.2 1.2
AM1
a PM3 ;1; 2l
M
~
1 ~
N '" 1 ~
rm <0
~ ~
0.8 M !ll
~
.... <0
0.8 Ie en
0.6 0.6
0.4 0.4
0.2 0.2
o500 o
1000 1500 2000 2500 3000 3500 500 1000 1500 2000 2500 3000 3500
1 1.4  ,             . ,
796 MNDO MNDOd
2075
1.2  668
0.8 3692
1 726
0.6 1478 1815
1166
0.8
1168
0.4 0.6
0.4
0.2 0.2
o o ~_r~r_~.__.~~
1000 1500 2000 2500 500 1000 1500 2000 2500 3000 3500 4000
500
• 1
Frequencies (em )
Fig. 14.4.
204 Quantum Mechanics  A Comprehensive Text for Chemistry
?H2CtN~SN
Ar N=tliR
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206 Quantum Mechanics  A Comprehensive Text for Chemistry
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derived from IN, N' bis(2'cyanoethyI) amino benzaldehyde", Kishor Arora, A.R.Khan
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Kishor Arora, Aarti Gupta and D.D. Agarwal, ASIAN 1. CHEM., 14, 1611 (2002).
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ligands", Kishor Arora, ASIAN J. CHEM., 14, 1719 (2002).
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carbonyl compounds ligands", Kishor Arora and Sonal Agnihotri, JOURNAL SAUDI
CHEM. SOC., Q, 445 (2002).
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some simple carbonyl compounds ligands", Kishor Arora and Sona1 Agnihotri, JOURNAL
SAUDI CHEM. SOc., 1,221 (2003).
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Burman, JOURNAL SAUDI CHEM. SOC .• 9(2), 297 (2005).
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Kishor Arora and Sonal Agnihotri, ORIENTAL J. CHEM .• 22(2), 315 (2006).
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Kishor Arora and Sonal Agnihotri, JOURNAL SAUDI CHEM. SOC. lOrll, 303 (2006).
Introduction to use of Computers in Quantum Mechanics 207
APPENDIX I
TABLE FOR PHYSICAL CONSTANTS
Constant Symbol S.I. Value
APPENDIX  II
TABLE FOR SOME ENERGY CONVERSION FACTORS
1 erg = 107 J
1J = 107 erg
1 cal =4.184J
1 ev = 1.602 x 10 19 J
1 ev = 1.602 x 1012 erg
1 ev = 23.06 k cal/mol
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