CHE 101G GENERAL CHEMISTRY (For Genetics Engineering and Biotechnology)

3 Hours/Week, 3.0 Credits

1. Electronic Structure: Quantum theory, atomic spectrum of hydrogen and the Bohr
model, Quantum numbers, Concept of Energy levels and atomic orbital, Electronic
configuration, Chemical bonding and molecular structure.
2. The periodic Table: Development of the periodic table, Electron arrangements and
the periodic table, Summarized chemical properties of s-block, p-block and d-block
elements.
3. Introduction to Thermodynamics: The Basic Concepts: Systems and surroundings,
State and state functions, Equilibrium states and reversibility, Energy, Heat and work.
The First Law: Statement and formulation, Derivation of expression for expansion work
and its application at different conditions, Heat capacity. Relation between Cp & Cv.
4. Acids and Bases: Theories and Modern definition of acids and bases, Dissociation
constant, strength, pH, Buffer solution etc.
5. Gaseous state: Measurement on gases, the ideal gas law, Volumes of gases
involved in reactions, Gas mixtures, Partial pressure, Kinetic theory of gases, Real
gases.
6. Introduction to Chemical Kinetics: Rate laws, rate constant, equilibrium constant,
order of reaction etc.
7. Organic Chemistry: Introduction, Classification, Nomenclatures, preparations and
Properties (Physical & Chemical) of (i) Aliphatic and aromatic hydrocarbons, (ii)
Aldehydes and ketones, (iii) Carboxylic acids and (iv) Alcohols and phenols (v)
Carbohydrates (mono- and disaccharides).
5. Gaseous state: Measurement on gases, the ideal gas law, Volumes of
gases involved in reactions, Gas mixtures, Partial pressure, Kinetic theory
of gases, Real gases.
Deriving Ideal Gas Equation

• From Boyle’s Law: 1

V
p
• From Pressure Law: V  T

• From Avogadro’s Law:V n

nT
Combining these three: V
p

Rewriting using the gas constant R:

 nT 
V  R  Therefore:- pV  nRT
 p 
 The numerical value of R

pV  nRT

The volume occupied by 1 mole of a gas at a given pressure and a given

temperature.
Therefore:- P  V mole
R
T
force volume mole 1
 
area temperatur e
force (length) 3 mole 1
 2

(length) temperatur e

mole 1
 force  length
temperatur e
work  mole 1
  energy mole 1 K 1
temperatur e
The numerical value of R

a) Litre-atmosphere units:

R  0.0821 L - atm K -1 mole -1

b) C.G.S units:

R  8.316  107 ergs K -1 mole -1

c)Calories:

R  1.987 calories K -1 mole -1

b) Joules:

R  8.316 J K -1 mole -1
Behaviour of real gases: the Amagat’s Curves

• Assumptions in kinetic theory of gases not always valid

particularly at high pressures and low temp. This was
expertimentally established by Regnault, Amagat and others.
– Molecules are not infinitely small
– Attractive and repulsive forces are not negligible.
– Collisions are not always elastic.
Deviations from ideality: Compressibility Factor
The extent to which a real gas departs from ideal behaviour expressed by a function called
Compressibility factor, Z defined as

PV
Z
RT PV
• for one mole of an ideal gas (n=1). PV/RT always = 1. n
RT
• However, for real gases, PV/nRT doesn’t always = 1.
PV
• Ideal gas equation is better in some regions than in others. 1
RT
 Effects of pressure variation on deviation:

At very low pressure(up to 10 atm), for

all these gases Z is approximately equals to 1
indicating ideal behavior.

As the pressure is increased, N2 and CO2

shows a continuous increase in Z (from 1 ). For
N2 and CO2, first decreases, passes through a
minimum and then increases with pressure.

For CO2, the dip in the curve is greatest as it is easily

liquefiable. Fig. Z vs P for H2, N2 and CO2 at 300 K
Mean Free Path:
Average distance a molecule travels between two successive collisions.
Postulates of the kinetic theory of gases

1. A gas consists of tiny particles called molecules (atoms in few cases)

2. Molecules are treated as points having no volume.
3. Molecules move continuously and randomly.
4. Molecules collide with each other changing direction and velocity.
5. Collision with the walls of the container exert a force, which is pressure.
6. The collisions are elastic ( no loss of kinetic energy).
7. In the perfect gas there are no attractive or repulsive forces between
molecules.
Derivation of the kinetic gas equation

The pressure exerted by a gas is the total effect of the impacts of the gas
molecules on the walls of the container. The expression for the pressure of a gas in
terms of the molecular velocity may be derived as follows:

Consider a cube with sides l cm each, which contains n molecules of a gas,

the mass of each molecules being m.

l
Y
l
l
v
B A u
X
w
Z
Fig. A cube with side l cm each
 l Y
l l
v
B A u
X
w
Z
Fig. A cube with side l cm each

Let the root mean square velocity of the molecules be c. This may be
resolved inti three mutually perpendicular components u, v and w along the x, y
and z xes respectively. C and its components are related by the expression

c 2  u 2  v 2  w2
The molecules are moving random within the containerand are colliding with each
other and the walls of the container.

Consider onn emolecule starting from the wall B and moving in a stright line
perpendicularly to the wall opposite to it and rebounds.
 l Y
l l
v
B A u
X
w
Z
Fig. A cube with side l cm each

The momentum of the molecule before impact with the wall A = mu

The momentum of the molecule after the impact with the wall A = -mu
Therefore, change in momentum = mu –(-mu) = 2mu

This will the momentum imparted to the wall by each impact. Before the molecule
can strike the wall A again it has to travel a distance 2l to the face B and back.

The time required to travel from A to B and back to A = 2l/u secodns.

Therefore, the number of impactson th all A by e time required to travel from A to B
Therefore, the number of impacts on the wall A by one molecule in one seconds
will be u/2l.
The total change in momentum per second for molecule due to impacts with wall A
= 2mu.u/2l = mu2/l

As the number of molecule is n the total change to momentum in one second for all
the molecules = mnu2/l.

The rate of change of momentum = Force ( on the wall A)

Force f = mnu2/l

Experiments shows that the force exterted on the alls is the same for all the walss.
Hence the velocitiws resolved along three axes must be equal. i.e.

u 2  v 2  w 2  c 2  3u 2
2
c
or u 2 
3
 mnc 2
Therefore, force  f 
3l
c2
or u 
2

3
Dividing both sides by l2
f mnc 2
or 2 
l 3l 3
f
But 2 is force per unit area which is equal to pressure, P
l 3
l = Volume , Volume of the container cube.

Hence
mnc2
P
3V
1
or PV  mnc 2
3
This is the kinetic gas equation for gases
 Although the above deduction has been madee for a cubical vessel the equation is
valid for a vessel of any shape as the vessel can be divided into a large number of
small cubes for which this equation is valid.
Deduction of the gas laws from the kinetic gas equation

Boyle’s law:

Kinetic gas equation can be re written as

1 2 1 2
PV  mnc   mnc   total kinetic energy
2 2

3 3 2 3
1 2
Since the kinetic energy of a moving body is 2 mc . For a given
quantity of gas , when the temperature is constant, the kinetic energy
is constant.
Temperature is a measure of the kinetic energy of the molecules, the higher the
temperature the higher is the kinetic energy of the molecules.
Charles’ law:

The total kinetic energy of the molecules is proportional to the absolute

temperature. i.e. K.E. = const x T

1 2 1 2
PV  mnc   mnc   total kinetic energy
2 2

3 3 2 3

PV  const .  T

At constant volume for a given quantity of gas P T

Charles’ law.
Avogadro’s law:
Consder two gases are at the same pressure, P, and contained in vessels of equal
volume V, . Both the vessels are a the same temperature.

P ,V, T

1 2 1 2
PV  n1m1c1 PV  n2 m2 c2
3 3
Since P, V and T are same for the two gases, we can write

1 2 1 2
n1m1c1  n2 m2 c2 (1)
3 3
At the same temperature the kinetic energies of the molecules of both the gases
are the same.
1 2 1 2
m1c1  m2 c2 (2)
2 2
Divide eq. 1 by eq.2 gives

1 2 1 2
n1m1c1 n2 m2 c2
3 3
1 2 1 2
m1c1 m2 c2
2 2
or n1  n2

The number of molecules in equal volumes of the two gasesunder the

same condition of T and P is the same.

Avogadro’s law
Explanation of deviation: Van der Waals Equation

Volume correction:
Van der waals assumed that molecules of a real gas are rigid spherical particles
which posses a definite volume.

Volume of real gas = ideal volume – volume occupied by gas molecules

Volume of real gas = ideal volume – volume occupied by gas molecules

= V-b

For n moles of the gas, the corrected volume : = V - nb

For b is called Excluded Volume which is constant and characteristics for

each gas.

Pressure correction:
A molecule in the interior of a gas is attracted by other molecules on all
sides.
These attractive forces cancel out.
But for a molecules about to strike the wall of the vessel is attracted by
molecules on one side only. Hence it experiences an inward pull.

zero-point
energy for
harmonic
oscillator

Therefore it strikes the wall at reduced velocity.

Actual pressure of the gas , P, will be less than ideal pressure pideal. Then, .

P  Pideal  p
Reduced pressure
Pideal  P  p
P is determined by the force of attraction between molecules (A) striking the
wall of the container and the molecules (B) pulling them inward.

The net force of attraction

p  C A  CB
n n
p  
V V
an 2
p  2
V
Where a is proportionality constant charecteristics of the gas.
Thus, the pressure in the ideal gas equation is corrected as

Pideal  P  p
an 2
Pideal  P  2
For n mole of gas
Van der waals equation: an 2
(P  2 ) (V  nb)  nRT
V

a
For 1 mole of a
(P  2 ) (V  b)  RT
V
gas
Where a and b are called Van der Waals constant

Significance of a and b:
Gas like hydrogen which is difficult to liquefy have low values of a. where as
easily liquefiable gas like ammonia has high value of a.

the constant a is thus a measure of a magnitude of intermolecualr attraction.

The value of b is lowest for hydrogen and highest for sulfur dioxde indicating
that b is a measure of the sixe of the molecule.
Critical Temperature and Pressure
Critical Temperature

Gases can be converted to liquids by compressing the gas at

a suitable temperature.
Gases become more difficult to liquefy as the temperature Microscopic view of a gas
increases because the kinetic energies of the particles that
make up the gas also increase.

The critical temperature of a substance is the temperature

at and above which vapor of the substance cannot be
liquefied, no matter how much pressure is applied.
Microscopic view of a liquid
Every substance has a critical temperature. Some examples
are shown below.

substance critical temperature (oC)

NH3 132
O2 -119
CO2 31.2
H2O 374
Critical Pressure
The critical pressure of a substance is the pressure required to liquefy a gas at its critical
temperature. Some examples are shown below.

substance critical pressure (atm)

NH3 111.5
O2 49.7
CO2 73.0
H2O 217.7
 [A]
ln   kt
[A]0
[A]
 e  kt
[A]0

[A ]  [A ]o e  kt

This is the integrated rate equation for first order reaction.

To test it: Plot

slope   k
ln ([A]
ln ([ A]   k t  ln[ A]0

Y mx + c
time (t)
 So to the test if the reaction is a first order, plot the natural logarithm (ln) of a
reactant conc (ln A) versus time and see whether th egraph is linear.

If the graph is linear and has a negative slope, the reaction must be of first order.

[A]
 ln  kt  ln
[A] slope  k
[A ]0 [A] o

time (t)

Examples of first order reaction

H2O2(l) H2O+ 1/2 O2(g)

2N2O5(g) 4NO2(g) + O2(g)

To convert this frequency to wavenumber, the unit most usually employed in
vibrational spectrsocopy, we must divided by the velocity of light, c, expressed in
cm-1, obtaining
1 k
osc.  cm-1 .......(3.4)
2πc μ

Vibrational energies like all other molecular energies are quantized,

and the allowed vibrational energies for any particular system
may be calculated from the Schrödinger equation.

For the simple harmonic oscillator this turn out to be

1
Ev  (v  )hωosc. joules (v  0,1, 2,3...) .......(3.5)
2
where v is called the vibrational quantum numbers
Ev 1
Converting to the spectroscopic units, cm , we have: εv 
-1  (v  )osc. cm
-1

hc 2
.......(3.6)
As the only energies allowed to a simple harmonic vibrator.
Some of these allowed energies are shown in Fig. 3.2 below:
Lowest vibrational energy:

The lowest vibrational energy can be obtained by puttingv = 0 in eq.

3.5 or 3.6, is
1
E0  hωosc. joules (ωosc. in Hz )
2
.......(3.7)
1 -1
or ε0  osc. -1
cm ( osc.in cm )
2
Therefore, the diatomic molecule (and, indeed, any molecule) can
never have zero vibrational energy; the atoms can never be completely
at rest relative to each other.

1 1
or osc.
-1
The quantity hωosc. joules cm is known as the zero-point energy.
2 2

It depends on the classical vibration frequency and hence on the

strength of the chemical bond and the atomic masses.
Prediction of zero-point energy is the basic difference between the wave
mechanical and classical approaches to molecular vibrations. Classical
mechanics could find no objection to a molecule possessing no
vibrational energy but wave mechanics insist that it must always
vibrate to some extent; the latter concussion has been amply borne out
by experiment.

Selection rule:
Schrödinger equation led to the simple selection rule for the harmonic
oscillator undergoing vibrational changes:

v  1 .......(3.8)

Applying this selection rule, we have for emission:

1 1
εv  1  v  (v  1  )osc.  (v  )osc
2 2
 osc. cm -1 .......(3.9a)
and for absorption:

εv  v  1  osc. cm-1 .......(3.9b)

Vibrational levels are equally spaced, transitions between any

two neighbouring states will give rise to the same energy
change.

Q. Explain the selection rules for IR absorption under harmonic

approximation.
Some of these allowed energies are shown in Fig. 3.2 below:
3.1.3 The anharmonic oscillator
Real molecules do not obey exactly the laws of simple harmonic motion;
real bonds although elastic, are not so homogeneous as to obey Hooke's law.
If the bond between atoms is stretched, for instance, there comes a point
at which it will break and the molecules dissociated into atoms.
Therefore for small compression and extension the bond may be taken as
perfectly elastic, for larger amplitudes, say greater then 10 % of the
bond length, a much more complicated behavior must be assumed.

Anharmonic motion: when the restoring force is not

proportional to the displacement
As the two atoms approach one another, coulombic repulsion between the
two nuclei produces a force that acts in the same direction as the restoring
force of the bond. For this reason, the potential energy can be expected to
rise more rapidly than the harmonic approximation predicts.
- At the other extreme of oscillation, a decrease in the restoring force, and
thus the potential energy, occurs as the interatomic distance approaches that at
which dissociation of the atoms takes place.
Morse curve/function:
Fig. 3.3 shows the shape of the energy curve for a typical diatomic
molecule, together with (dashed) the ideal, simple harmonic parabola.
A purely empirical expression which fits this curve to a good approximation
was derived by P.M.Morse, and is called the Morse function:

E  Deq.[1  exp{a(req. - r)}] 2

.......(3.11)

Where a is a constant for a particular molecule and D eq. is the dissociation

energy.
Vibrational energy levels for anharmonic oscillator:

When Eq. 3.11 is used instead of Eq. 3.2 ( for harmonic oscillator) in the
Schrödinger equation, the pattern of the allowed vibrational energy levels is found
to be
anharmonic E  Deq.[1  exp{a(req. - r)}] 2 .......(3.11)

1
harmonic E  k(r - req.) ..............(3.2)
2
1 1 2 -1
εv  (v  )e - (v  ) exe cm (v  0,1, 2,3...) (3.12)
2 2
Anharmonicity constant
where e is an oscillation frequency (expressed in wavenumbers) and xe is
the corresponding anharmonicity constant which, for bond stretching
vibrations, is always small and positive (0.01).
Therefore the vibrational energy levels for anharmonic
oscillator crowd more closely together with increasing v (Fig.
 If we re write eq. 3.12 for anharmonic oscillator as

 1  1
εv  e 1 xe(v  ) (v  ) (3.13)

 2  2
Comparison with harmonic oscillator:

1
εv  (v  )osc. (3.6 )
2
Therefore,
1 
 1  1
(v  )osc.  e 1 xe(v  ) (v  )
2 
 2  2

 1 
or, osc.  e 1 xe(v  )  (3.14)

 2 
Thus, the anharmonic oscillator behaves like the harmonic oscillator but
with an oscillation frequency that decreases steadily with increasing
vibrational quantum number v. (Question)
 1 1 2
εv  (v  )e - (v  ) exe
2 2
Harmonic term Anharmonic
term
exe
is usually positive,
so vibrational levels
get close together

Fig. 3.4 the vibrational energy levels and some transitions between them for a
diatomic molecule undergoing anharmonic oscillation.
Zero point energy for anharmonic oscillator:
v =0
The lowest vibrational energy can be obtained by putting in eq.
3.14

 1 
osc.  e 1 xe(v  )  (3.14)

 2 
 1  -1
 0  e1- xe)  cm zero-point
 2  energy for
harmonic
And, 
 1  1
εv  e 1 xe(v  ) (v  ) (3.13) oscillator

 2  2 1
osc. cm
-1

1  1  -1 2
ε 0  e 1 xe  cm
2  2 

zero-point energy.
Therefore, zero point energy for anharmonic oscillator differ slightly
from that for harmonic oscillator.
Selection rule for anharmonic oscillator
Schrödinger equation led to the selection rule for the anharmonic
oscillator undergoing vibrational changes:

v  1,  2,  3,... etc

Thus they are the same as for harmonic oscillator with the additional
possibility of larger jumps.

At higher quantum numbers, E gets smaller, and the ( = +/-1)

selection rule can be broken

Double ( = +/-2), triple ( = +/-3), and higher order

transitions can occur, leading to overtone bands.
Population in Vibrational energy levels: Boltzmann
distribution
Background:

The intensity of a transition from one quantum state to another resulting

from the interaction of electromagnetic radiation with a molecule is not
only dependent:

• on matching the energy of the radiation with differences in

molecular energy levels and
• selection rules governing allowed transitions;

but is also dependent on the number of molecules populating the

initial state in the transition.

The Boltzmann distribution tells us how the internal energy, U of a

system is distributed amongst the various energy levels of the system.

The dynamic modes into which the internal energy can be distributed are:
translation-, rotation-, vibration- and electron-energy.
To a good approximation, sinceXe  0.01, the three spectral lines lie very close to

e, The line near it is called fundamental absorption

2e, The line near it is called first overtones
3e The line near it is called second overtones
Hot bands:

Although we have ignored transitions from =1 to higher states, we

should note that, if the temperature is raised or if the vibration has a
particular frequency, the population of the =1 state may become
appreciable. Thus at, say, 600 K (300°C)
Nv  1
 exp 2.4  ≈ 0.09
Nv  0

Therefore, the transition from  =1 state to  =2 will be some 10% the

intensity of those from  =0 state to  =1.
 A similar increase in excited state population would arise if the
vibrational frequency were 500 cm-1 instead of 1000 cm-1. The wave
number for the hot band transition is:

4. v  1  v  2 , v  1, normaly very week

ε  εv  2 - εv  1
1 1  1 1 
 2 e - 6 xee - 1 e - 2 xee  (3.15d)
2 4  2 4 
 e (1  4 xe) cm  1

At slightly lower wavenumber than the fundamental (since Xe is small

and positive)
such week absorptions are usually called Hot
bands

hot because a high temperature is one condition for this occurrence.

Combined Vibration-Rotation Spectra

Of course, diatomic molecules do not remain stationary as they undergo

vibration; they also rotate through space. The rigid rotor model may be
used to approximate the rotational contribution to the IR spectrum of a
diatomic molecule
3.2 the diatomic vibrating rotator
For a typical diatomic molecule:

Rotational energy separation Vibrational energy separation

1-10 cm-1 for HCl is nearly 3000 cm-1

Since energies are different, a diatomic molecule can execute rotation

and vibration quite independently

Born-Oppenheimer approximation

The combined rotational and vibrational energies is simply the sum of the
separate energies:
Etotal  Erot  Evib (joules)
εtotal  εrot  εvib (cm-1)
Taking the separate expressions for εrot and εvib, we have

εj, v  εj  εv
 BJ(J  1)  DJ 2 (J  1) 2  HJ 3 ( J  1) 3  ...
1 1 2
 (v  )e - xe(v  ) e cm -1 (3.17)
2 2

If we ignore small distortion constant D, H, etc, then

εtotal  εj, v  εj  εv  BJ(J  1)  (v  12 )e - xe(v  12 ) 2e cm

-1
(3.18)

The rotational energy levels are sketched in Fig. 3.5 for the two lowest
vibrational levels.

However, it is not completely logical to ignore D since this implies that

we are treating the molecule as rigid yet vibrating !!. The retention of
D would have a minor effect on the spectrum.
Fig. 3.5 Some of the vibrational energy levels for the first two vibrational states
of a diatomic molecule
Selection rule for combined motion:

Same as for each separately

v  1,2, etc. J  1 .......(3.19)

Transitions between the rotational-vibrational energy levels:

Considering only v  0  v  1 the transition we have in general:

ε j,v  εj' , v  1 - εj" , v  0

1 1 2
εj, v  BJ(J  1)  (v  2 )e - xe(v  2 ) e cm
-1
(3.18)

1 1 2  1 1 2 

 BJ' (J' 1)  (1  )e - xe(1  ) e -  BJ" (J" 1)  (0  )e - xe(0  ) e 
2 2  2 2 

1 1  1 1 
 BJ' (J' 1)  1 e - 2 xee -  BJ" (J" 1)  e - xee 

2 4  2 4 
  1 1 1 1  
 1 e - e  xee - 2 xee   BJ' (J' 1) - BJ" (J" 1)
 2 2 4 4 

 e - 2 xee   B(J'  J" )(J'  J" 1)

 e (1 - 2 xe)   B(J'  J" )(J'  J" 1)

-1
  0  B(J'- J" )(J'  J" 1) cm

where,  0  e(1- 2 xe)

ε j,v   0  B(J'- J" )(J'  J" 1) cm

-1
Now we can have:

1. J  1, that is J'  J" 1 or J'  J"  1; hence

ε j,v   0  B(J'- J" )(J'  J" 1) cm

-1

-1
  0  B(J" 1  J" 1) cm

-1
  0  2 B(J" 1) cm J"  0,1,2,... (3.20a)

2. J  1, that is J"  J' 1 or J'  J"  1; hence

ε j,v   0  B(J'- J" )(J'  J" 1) cm

-1

-1
  0  B(J'  J' 1  1) cm

-1
  0  2 B(J' 1) cm J'  0,1,2,... (3.20b)
These two expressions may conveniently be combined into:

ε j,v  vspect.   0  2Bm cm

-1
m  1,  2 ,... (3.20c)

The above eq represents the combined vibration-rotation spectrum.

where m replacing (J" 1) in eq. 3.20a and (J' 1) in eq. 3.20b.

-1
  0  2 B(J" 1) cm J"  0,1,2,... (3.20a)

-1
  0  2 B(J' 1) cm J'  0,1,2,... (3.20b)

Important note: m cannot be zero since this would imply values of

or
J'
J"
to be -1.

The frequency  0 is usually called the band origin or band center.

 ε j,v  vspect.   0  2 Bm cm
-1
m  1,  2 ,... (3.20c)

combined vibration-rotation spectrum

 It consists of equally spaced lines (spacing = 2B) on each side of

the band origin.

 Since m  0 the line at  0 (band origin) itself will not appear.

 Lines to the low frequency side of corresponding to

0
negative
m(
J  1 ) are referred to as the P branch

 while those to the high-frequency side (m positive ΔJ  1)

are called the R branch.

The P and R notation is illustrated on the diagrammatic spectrum in Fig.

3.6.
 cm-1
Fig. 3.6 Some transitions between the rotational-vibrational energy levels of a
diatomic molecule, together with spectrum arising from them.
Dissociation of a molecule and vibrational quantum number:

A diatomic molecular dissociate when ε approaches zero.

Separation between the adjacent vibrational energy levels is given by

v  v 1 ε  εv  1 - εv
1 1 2
εv  (v  )e - xe(v  ) e
2 2
cm
-1
(3.18)

1 1 2  1 1 2 
 BJ' (J' 1)  (1  )e - xe(1  ) e -  BJ" (J" 1)  (0  )e - xe(0  ) e 
2 2  2 2 

1 1  1 1 
 BJ' (J' 1)  1 e - 2 xee -  BJ" (J" 1)  e - xee 

2 4  2 4 

The separation decreases with increasing vibrational quantum number v and

ε
the dissociation limit is reached when approaches zero. Thus the
maximumvvalue of isv given
max by , where
Separation between the adjacent vibrational energy levels is given by

v  v 1 ε  εv  1 - εv
1 1 2
ε v  (v  )e - xe(v  ) e cm
2 2
-1
(3.18 )

ε 1 1 2  1 1 2 
  -1
 (v  1  )e - xe(v  1  ) e - (v  )e - xe(v  ) e  cm
2 2  2 2 

ε  (v  1  2  v  2 )e  exe(v  2 )  (v  1  2 ) 
1 1  1 2 1 2 


 

ε  e  exe  2  2v
 e 1  2 xe(v  1) 
At dissociation point ε  e 1  2 xe(vmax  1)   0
 e  2exe(vmax  1)  0
2e xe(vmax  1)  e
e
(vmax  1) 
2e xe
1
(vmax  1) 
2 xe
Since the anharmonicity constant is of the order of 10 -2, it follows that
1
(vmax  1)   50 vmax  49
2  .01
Question: Show that a diatomic molecule dissociate into atoms if it is
present in a vibrational state of vibrational quantum number
1
(vmax  1) 
2 xe
The diagram shows a portion of the potential diagram for a stable electraonic state of a
diatomic molecule. That electronic state will have several vibrational states associated
with it, so that vibrational spectra can be observed. Most commonly, rotational
transitions which are associated with the ground vibrational state are observed.
 The Schrödinger equation
In quantum mechanics, the Schrödinger equation is an equation that describes
how the quantum state of a physical system changes with time. It was formulated
in late 1925, and published in 1926, by the Austrian physicist Erwin Schrödinger.
In classical mechanics, the equation of motion is Newton's second law., and
equivalent formulations are the Euler-Lagrange equations and Hamilton's equations. In
all these formulations, they are used to solve for the motion of a mechanical
system, and mathematically predict what the system will do at any time beyond
the initial settings and configuration of the system.
In quantum mechanics, the analogue of Newton's law is Schrödinger's equation for
a quantum system, usually atoms, molecules, and subatomic particles; free, bound,
or localized.
Newton's second law

The change of momentum of a body is proportional to the impulse impressed

on the body, and happens along the straight line on which that impulse is
impressed. If a force generates a motion, a double force will generate double
the motion, a triple force triple the motion, whether that force be impressed
altogether and at once, or gradually and successively.
 Frequency is the number of occurrences of a repeating event per unit time. It is also
referred to as temporal frequency. The period is the duration of one cycle in a
repeating event, so the period is the reciprocal of the frequency. For example, if a
By counting
newborn baby's heart beats at a frequency of 120 times a minute, its period (the
Calculating the frequency
interval between beats) of a repeating
is half a second.event is accomplished
by counting the number of times that event occurs within a
specific time period, then dividing the count by the length of
the time period. For example, if 71 events occur within 15
seconds the frequency is:

Sinusoidal waves of various frequencies; the bottom waves have

higher frequencies than those above. The horizontal axis represents
time.
 Frequency is the number of occurrences of a repeating event per unit time. It is also
referred to as temporal frequency. The period is the duration of one cycle in a
repeating event, so the period is the reciprocal of the frequency. For example, if a
By counting
newborn baby's heart beats at a frequency of 120 times a minute, its period (the
Calculating the frequency
interval between beats) of a repeating
is half a second.event is accomplished
by counting the number of times that event occurs within a
specific time period, then dividing the count by the length of
the time period. For example, if 71 events occur within 15
seconds the frequency is:

Sinusoidal waves of various frequencies; the bottom waves have

higher frequencies than those above. The horizontal axis represents
time.
Vibrations in molecules can be excited by the application of radiation at the same frequency
as the vibration itself. This gives rise to spectroscopic methods of studying molecular
structure, which depend upon being able to predict or at least rationalise the vibrations that
are observed. Symmetry considerations play an important role in this.

Note that there is only one possible mode of vibration for a diatomic molecule, stretching (or
compression) of the bond. No bending modes exist, as neither end of the molecule has a fixed
position that is defined by being attached to another atom.
For polyatomic molecules there are multiple vibrational modes, because all of the bonds may
stretch or compress, and bond angles may also change, allowing the existence of bending
modes.

For a non-linear molecule containing N atoms, there are 3N - 6 independent vibrational

modes. If the molecule is linear, there are 3N - 5 modes of vibration:

Each atom may be displaced in any one of three directions (x, y, z), giving 3N possible
displacements. Three coordinates are required to specify the location of the centre of mass of
the molecule (fixing the location of the molecule in space). Further, three angles are needed
to specify the orientation of a non-linear molecule in space. These six pieces of information
restrict the possible vibrational modes to 3N - 6.
(Alternatively, the situation can be viewed as follows. There are 3N possible vibrational
modes. However, if all the atoms are vibrating so that they move in the positive x direction,
then this is actually a translation of the whole molecule through space in the x direction, with
no change in the bond lengths or angles of the molecule. This does not count as a vibration.
Similar remarks can be made about translations in the y and z directions. This reduces the
number of vibrational modes by three. Similarly, it is possible for the atoms to vibrate
together in such a way that the molecule is actually rotating rather than vibrating. Rotation
can occur about any of the three Cartesian axes, so a further three of the possible vibrations
are counted as rotations not vibrations. Thus of the 3N possible vibrations, 3 are translations,
3 are rotations and 3N - 6 are vibrations.)

For a linear molecule, only two angles are required to specify the orientation in space (the
infinite rotational symmetry about the molecular axis means that all possible orientations
about this axis are equivalent), hence there are 3N - 5 vibrations. (In terms of the alternative
view of the situation, no vibrational motion of the atoms in a linear molecule can lead to
rotation about the axis of the molecule, so one of the rotational modes is not counted.)
It is necessary for more advanced calculations to find a way of describing the modes (in terms
of the different atomic motions that they represent). It proves simplest to do this in terms of
the normal modes of a molecule. Normal modes are the independent, synchronous motions
of atoms or groups of atoms that may be excited without exciting other normal modes. For
example, the symmetric and antisymmetric stretches of CO2 , in which the oxygen atoms are
displaced while the carbon atom remains stationary, are two of the normal modes of the
molecule:
Symmetrical stretching Asymmetrical Scissoring (IR
(IR inactive) stretching (IR active) inactive)

Rocking (IR active) Wagging (IR active) Twisting (IR inactive)

• Qualitatively, the curves take the anharmonic form
which depart from harmonic behavior by varying
degrees, depending on the nature of the bond and the
atoms involved.
Note, however, that the harmonic and anharmonic curves
are nearly alike at low potential energies.
Anharmonicity leads to deviations of two kinds:
1) At higher quantum numbers, E becomes smaller and
the selection rule is not followed.
• As a result, weaker transitions called overtones are
sometimes observed. These transitions correspond to
 =  2 or  3.
• The frequencies of such overtone transitions are:
• Approximately two or three times that of the
fundamental frequency
• The intensities are lower than that of the fundamental
frequency.
2) Different vibrations in a molecule can interact to give
absorption peaks with frequencies that are
approximately sums or differences of their
fundamental frequencies (combination frequencies)

• The Intensities of overtone, combination and

difference peaks are lower than that of the
fundamental frequency.
• . Anharmonic Oscillator

55
Diatomic molecules: Can only vibrate by
stretching the bond between the atoms.

Polyatomic molecules: The bonds can also

bend.