PHYSICAL CHEMISTRY – FIRST QUESTION PAPER (PHYSICAL CHEMISTRY 1st que ppr.

pdf)

SECTION – I (COMPLETE)

Q1 a) Answer any four [8 marks, 2 marks each]

i) What are the physical significances of ψ and ψ²? [2]

Answer:

In quantum mechanics, the state of a par cle is completely described by a wave func on ψ(x, t).

Physical significance of ψ (wave func on):

 ψ itself is not directly measurable. It is a complex func on that contains all possible
informa on about the quantum system.

 The wave func on evolves determinis cally according to the Schrödinger equa on.

 ψ can be posi ve, nega ve, or complex. Only the square of its modulus has direct
physical meaning.

 The phase of ψ is important for interference effects.

Physical significance of ψ² (probability density):

 For a normalized wave func on, the quan ty |ψ|² dτ gives the probability of finding the
par cle in the volume element dτ.

 Mathema cally: ∫ |ψ|² dτ = 1 over all space.

 The probability of finding the par cle in a finite region from x₁ to x₂ is: P = ∫_{x₁}^{x₂}
|ψ|² dx.

 |ψ|² is always real, non-nega ve, and represents the spa al distribu on of the par cle.

 In experimental measurements (e.g., electron density maps), the quan ty measured is

propor onal to |ψ|².

Example: For the ground state of a par cle in a 1D box, ψ₁(x) = √(2/L) sin(πx/L).
Then |ψ₁|² = (2/L) sin²(πx/L), which is maximum at the center (x = L/2) and zero at the walls.

Thus, while ψ is a mathema cal tool, ψ² provides a direct probabilis c interpreta on of where
the par cle is likely to be found.
ii) What do you mean by chemical poten al? [2]

Answer:

Defini on:
Chemical poten al (μ) is the par al molar Gibbs free energy. It is defined as:

μ_i = (∂G/∂n_i){T, P, n{j≠i}}

It represents the change in Gibbs free energy when one mole of a component i is added to a
large system at constant temperature and pressure, while keeping the amounts of all other
components constant.

Physical interpreta on:

 μ is the escaping tendency of a substance from a phase.

 At equilibrium, the chemical poten al of each component is the same in all phases
present.

 For a pure substance, μ = G_m (molar Gibbs free energy).

Dependence on concentra on:

For an ideal gas: μ = μ° + RT ln(P/P°).
For an ideal solu on: μ_i = μ_i° + RT ln x_i.

Applica ons:

 Predicts direc on of mass transfer (from higher μ to lower μ).

 Determines equilibrium constants: ΔG° = –RT ln K.

 Phase equilibrium: μ_liquid = μ_vapor at boiling point.

 Used in Gibbs-Duhem equa on: Σ n_i dμ_i = 0 at constant T, P.

Thus, chemical poten al is central to thermodynamics of mixtures, phase equilibria, and

chemical reac ons.

iii) What is Hamiltonian operator? Give its significance. [2]

Answer:
Defini on:
The Hamiltonian operator (Ĥ) is the total energy operator in quantum mechanics. For a single
par cle in one dimension:

Ĥ = –(ħ²/2m) (d²/dx²) + V(x)

where the first term is the kine c energy operator and V(x) is the poten al energy.

For a system of par cles:

Ĥ = Σ [ –(ħ²/2m_i) ∇_i² ] + V(r₁, r₂, ..., r_N)

Significance:

1. Time-independent Schrödinger equa on:

Ĥψ=Eψ
The eigenvalues E are the allowed energy levels of the system. The eigenfunc ons ψ are
sta onary states.

2. Time evolu on of a quantum state:

iħ ∂ψ/∂t = Ĥ ψ
The Hamiltonian generates the me evolu on of the wave func on.

3. Measurement of energy:
The Hamiltonian corresponds to the observable of total energy. If a system is in an
eigenstate of Ĥ, measuring energy gives a definite value E.

4. Commuta on with other operators:

If Ĥ commutes with an operator Â, then the corresponding observable A is a constant of
mo on (conserved quan ty).

Example: For a free par cle (V=0), Ĥ = –(ħ²/2m) d²/dx². Its eigenfunc ons are plane waves
e^(ikx) with energy E = ħ²k²/2m.

Thus, the Hamiltonian operator is the most fundamental operator in quantum mechanics,
determining both allowed energies and me evolu on.

iv) Explain exact differen al. [2]

Answer:

Defini on:
A differen al form dF = M(x, y) dx + N(x, y) dy is said to be exact if there exists a state func on
F(x, y) such that:
M = (∂F/∂x)_y and N = (∂F/∂y)_x

Condi on for exactness (Euler's criterion):

(∂M/∂y)_x = (∂N/∂x)_y

This is because mixed par al deriva ves of F are equal: ∂²F/∂x∂y = ∂²F/∂y∂x.

Physical significance:

 If dF is exact, then F is a state func on – its change depends only on ini al and final
states, not on the path.

 Examples of exact differen als in thermodynamics: dU, dH, dG, dA, dS.

 Examples of inexact differen als (path func ons): dq (heat), dw (work).

Mathema cal property:

The line integral of an exact differen al around a closed loop is zero:
∮ dF = 0

Tes ng exactness example:

dU = T dS – P dV. Here M = T, N = –P.
Check: (∂T/∂V)_S = ? Should equal (∂(–P)/∂S)_V – this gives Maxwell rela ons.

Thus, the concept of exact differen al dis nguishes state func ons from path func ons, which
is fundamental in thermodynamics.

v) Give classical and quantum approach to Bohr's correspondence principle. [2]

Answer:

The correspondence principle (proposed by Niels Bohr) states that quantum mechanics must
reproduce classical physics in the limit of large quantum numbers.

Classical approach:

 For large n, the frequency of radia on emi ed in a transi on between adjacent energy
levels (n → n–1) should equal the orbital frequency of the electron in the Bohr model.

 For the hydrogen atom, energy E_n ∝ 1/n². The transi on frequency ν = (E_n – E_{n–
1})/h.

 As n → ∞, ν approaches the classical orbital frequency v/(2πr).

  This ensures that quantum theory does not contradict classical electromagne sm for
macroscopic systems.

Quantum approach:

 The expecta on value of posi on ⟨x⟩ for a quantum par cle should follow classical
equa ons of mo on (Ehrenfest's theorem).

 For a par cle in a box, the probability density |ψ_n|² oscillates rapidly for large n,
averaging to a uniform distribu on (classical result).

 For the harmonic oscillator, the quantum probability distribu on approaches the
classical distribu on as n increases.

 Quantum interference effects become negligible when de Broglie wavelength is much

smaller than system size.

Example: For a par cle in a 1D box, |ψ_n|² = (2/L) sin²(nπx/L). For large n, the oscilla ons
become so rapid that over any measurable interval, the average probability is 1/L – exactly the
classical result.

Thus, the correspondence principle bridges the gap between quantum and classical worlds.

Q1 b) Find ΔU and ψ if 2 moles of hydrogen at 3 atm pressure expand isothermally at 400°C

and reversibly to a pressure of 1 atm. [3]

Answer:

Given data:
n = 2 mol
P₁ = 3 atm
P₂ = 1 atm
T = 400°C = 400 + 273 = 673 K
Process: Isothermal, reversible expansion of an ideal gas (H₂).

Step 1: Change in internal energy (ΔU)

For an ideal gas, internal energy depends only on temperature.
Since the process is isothermal (ΔT = 0),
ΔU = 0 (J or kJ)

Step 2: Work done (W) by the gas

For isothermal reversible expansion of an ideal gas:
W = – nRT ln(V₂/V₁)
But from Boyle's law for isothermal process: P₁V₁ = P₂V₂ ⇒ V₂/V₁ = P₁/P₂

Thus: W = – nRT ln(P₁/P₂)

Subs tute values:

R = 8.314 J/mol·K (in SI units)
W = – 2 × 8.314 × 673 × ln(3/1)
ln(3) = 1.098612

W = – 2 × 8.314 × 673 × 1.098612

First: 8.314 × 673 = 5594.122
Then: 2 × 5594.122 = 11188.244
Then: 11188.244 × 1.098612 = 12290 J (approx.)

W = –12290 J
(The nega ve sign indicates work is done by the system on the surroundings.)

Step 3: Heat absorbed (q)

From the first law of thermodynamics: ΔU = q + W
With sign conven on (ΔU = q – W by system): Let's use ΔU = q – W (where W = work done by
system)

Since ΔU = 0: 0 = q – W ⇒ q = W = 12290 J

Step 4: The symbol ψ in the ques on

The ques on asks for "ΔU and ψ". In quantum chemistry, ψ is the wave func on, but here no
quantum system is specified. Possibly a misprint or refers to something else (work func on?
no).
Given the context, perhaps they mean q (heat). So answer: ψ = q = 12290 J.

Final answers:
ΔU = 0
ψ (heat absorbed) = 12290 J

Q2 a) A empt any three of the following [9 marks, 3 marks each]

i) Derive Schrödinger's me independent wave equa on. [3]

Answer:
Step 1: Start from classical energy equa on
For a par cle of mass m moving in a poten al V(r), the total energy is:

E = (p²/2m) + V(r)

Step 2: Introduce quantum mechanical operators

According to the de Broglie hypothesis, a par cle has wave-like proper es. In quantum
mechanics, the momentum operator is:

p̂ = –iħ ∇, where ħ = h/2π

The kine c energy operator becomes:

T = p̂ ²/2m = –(ħ²/2m) ∇²

Step 3: Write the me-independent Schrödinger equa on

Replace classical observables by operators ac ng on a wave func on ψ(r):

E ψ(r) = [ –(ħ²/2m) ∇² + V(r) ] ψ(r)

Rearranging:

–(ħ²/2m) ∇² ψ(r) + V(r) ψ(r) = E ψ(r)

This is the me-independent Schrödinger equa on (TISE).

Step 4: Interpreta on

 ψ(r) is an eigenfunc on of the Hamiltonian operator Ĥ = –(ħ²/2m)∇² + V(r).

 E is the corresponding eigenvalue (total energy).

 The equa on must be solved subject to boundary condi ons (e.g., ψ → 0 at infinity for
bound states).

 For a free par cle (V = 0), solu ons are plane waves ψ = e^(ik·r) with E = ħ²k²/2m.

Step 5: For one-dimensional problems

–(ħ²/2m) d²ψ/dx² + V(x) ψ = E ψ

This is the standard form used to solve problems like par cle in a box, harmonic oscillator, and
hydrogen atom.

Thus, the TISE is the fundamental equa on of quantum mechanics for sta onary states.

ii) What is expecta on value of posi on ⟨x̂⟩ for a par cle present in one-dimensional box? [3]
Answer:

System: Par cle in a 1D box of length L (0 < x < L).

The normalized wave func ons are:
ψ_n(x) = √(2/L) sin(nπx/L) , n = 1, 2, 3, ...

Defini on of expecta on value:

For an operator Â, the expecta on value in a state ψ is:
⟨Â⟩ = ∫ ψ* Â ψ dx

For posi on operator x̂ (mul plica on by x):

⟨x⟩ = ∫₀ˡ ψ_n*(x) · x · ψ_n(x) dx = ∫₀ˡ x |ψ_n(x)|² dx

Subs tute ψ_n:

⟨x⟩ = (2/L) ∫₀ˡ x sin²(nπx/L) dx

Use the integral formula:

∫ x sin²(ax) dx = x²/4 – (x sin(2ax))/(4a) – (cos(2ax))/(8a²)

Here a = nπ/L

Evaluate from 0 to L:

At x = L:
Term1: L²/4
Term2: – (L sin(2nπ))/(4a) = 0 (since sin(2nπ)=0)
Term3: – cos(2nπ)/(8a²) = –1/(8a²)

At x = 0:
Term1: 0
Term2: 0
Term3: – cos(0)/(8a²) = –1/(8a²)

Thus the definite integral = [L²/4 – 1/(8a²)] – [ –1/(8a²) ] = L²/4 – 1/(8a²) + 1/(8a²) = L²/4

Therefore:
⟨x⟩ = (2/L) × (L²/4) = L/2

Conclusion:
The expecta on value of posi on is L/2, the center of the box, independent of quantum
number n. This makes sense because the probability density |ψ_n|² is symmetric about the
midpoint for all n.
iii) Which of the following gives func ons as Eigen func ons for the operator d²/dx²? f(x) = 6x
and 5cos 2x. [3]

Answer:

Defini on: A func on f(x) is an eigenfunc on of an operator  if applying the operator yields a
constant mul ple of the same func on:
 f = λ f, where λ is the eigenvalue.

Operator: Â = d²/dx² (second deriva ve with respect to x)

Case 1: f(x) = 6x
First deriva ve: d/dx (6x) = 6
Second deriva ve: d²/dx² (6x) = 0

Now, 0 = λ × (6x).
For this to hold for all x, the only possibility is λ = 0 and the func on 6x must be the
eigenfunc on.
Since 0 = 0 × (6x), yes – it sa sfies the equa on with eigenvalue λ = 0.

Thus f(x) = 6x IS an eigenfunc on with eigenvalue 0.

Case 2: f(x) = 5 cos(2x)

First deriva ve: d/dx [5 cos(2x)] = –10 sin(2x)
Second deriva ve: d²/dx² [5 cos(2x)] = d/dx[–10 sin(2x)] = –20 cos(2x)

Now, –20 cos(2x) = λ × (5 cos(2x))

Divide both sides by 5 cos(2x) (for cos(2x) ≠ 0):

–20/5 = λ ⇒ λ = –4

Thus f(x) = 5 cos(2x) IS an eigenfunc on with eigenvalue –4.

Final answer: Both func ons are eigenfunc ons.

 6x → eigenvalue 0

 5 cos 2x → eigenvalue –4

iv) What are the postulates of quantum mechanics? [3]

Answer:

Quantum mechanics is built upon a set of fundamental postulates:

Postulate 1 (State of a system):
The state of a quantum system is completely described by a wave func on ψ(r, t).

 ψ must be single-valued, con nuous, and square-integrable (normalizable).

 |ψ|² dτ gives the probability of finding the par cle in volume element dτ.

Postulate 2 (Observables and operators):

Every physical observable (energy, momentum, posi on, etc.) is represented by a Hermi an
linear operator.

 Posi on: x̂ = x (mul plica on by x)

 Momentum: p̂ = –iħ ∂/∂x

 Energy (Hamiltonian): Ĥ = –(ħ²/2m)∇² + V(r)

Postulate 3 (Measurement and eigenvalues):

The only possible results of a measurement of an observable A are the eigenvalues a_n of the
corresponding operator Â.

 Â ψ_n = a_n ψ_n

Postulate 4 (Probability of measurement):

If the system is in a normalized state ψ, the probability of obtaining the eigenvalue a_n is
|⟨ψ_n|ψ⟩|², where ψ_n is the eigenfunc on corresponding to a_n.

Postulate 5 (Collapse of wave func on):

Immediately a er a measurement yielding a_n, the wave func on collapses to the
corresponding eigenstate ψ_n.

Postulate 6 (Time evolu on):

The wave func on evolves in me according to the me-dependent Schrödinger equa on:
iħ ∂ψ/∂t = Ĥ ψ

These postulates form the founda on of all quantum mechanical calcula ons and
interpreta ons.

Q2 b) Which of the following operators commute with each other? [3]

Given pairs:
i) [∂/∂x, x̂]
ii) [x̂, p̂x]
Answer:

Defini on: Two operators  and B commute if [Â, B] = ÂB – B = 0 (when applied to any wave
func on).

i) [∂/∂x, x̂*] – Assuming x̂* means mul plica on by x (posi on operator).

Test on an arbitrary wave func on ψ(x):

[∂/∂x, x] ψ = ∂/∂x (x ψ) – x ∂ψ/∂x

= (ψ + x ∂ψ/∂x) – x ∂ψ/∂x
=ψ

Since the result is ψ (not zero), the commutator is 1, not zero.

Thus [∂/∂x, x] = 1, so they DO NOT COMMUTE.

ii) [x̂, p̂x*] – Here p̂x = –iħ ∂/∂x is the momentum operator.
The fundamental commuta on rela on in quantum mechanics is:

[x̂, p̂x] = iħ

Since iħ ≠ 0, they DO NOT COMMUTE.

Final answer: Neither pair commutes.

Q3 a) A empt any two of the following [Marks: ~4–5 each]

i) Show that: (dT/dV)_S = – (dP/dS)_V and (dS/dP)_T = – (dV/dT)_P [5]

Answer:

First Maxwell rela on:

Start from the fundamental thermodynamic rela on for internal energy:

dU = T dS – P dV

Since U is a state func on, dU is an exact differen al. Therefore, the mixed par al deriva ves
must be equal:

∂/∂V (∂U/∂S)_V = ∂/∂S (∂U/∂V)_S

Now, from dU = T dS – P dV, we iden fy:
(∂U/∂S)_V = T
(∂U/∂V)_S = –P

Thus:
∂/∂V (T) = ∂/∂S (–P)

(∂T/∂V)_S = – (∂P/∂S)_V

Hence proved.

Second Maxwell rela on:

Start from the Gibbs free energy rela on:

dG = –S dT + V dP

G is a state func on, so dG is exact. Taking mixed par al deriva ves:

∂/∂P (∂G/∂T)_P = ∂/∂T (∂G/∂P)_T

From dG: (∂G/∂T)_P = –S

(∂G/∂P)_T = V

Thus:
∂/∂P (–S) = ∂/∂T (V)

– (∂S/∂P)_T = (∂V/∂T)_P

Rearranging:

(∂S/∂P)_T = – (∂V/∂T)_P

Hence proved.

These Maxwell rela ons are extremely useful in thermodynamics to replace unmeasurable
quan es with measurable ones (e.g., replacing (∂S/∂V)_T with (∂P/∂T)_V).

ii) Derive the Gibbs-Duhem Equa on. [5]

Answer:

Step 1: Euler's theorem for homogeneous func ons

The Gibbs free energy G is a homogeneous func on of the first order in the numbers of moles
n_i. By Euler's theorem:
G(T, P, n_i) = Σ n_i (∂G/∂n_i)_{T,P,n_j} = Σ n_i μ_i

where μ_i is the chemical poten al of component i.

Step 2: Take the total differen al of G in terms of μ_i

dG = Σ μ_i dn_i + Σ n_i dμ_i

Step 3: Compare with thermodynamic expression for dG

From thermodynamics:
dG = –S dT + V dP + Σ μ_i dn_i

Equa ng the two expressions for dG:

Σ μ_i dn_i + Σ n_i dμ_i = –S dT + V dP + Σ μ_i dn_i

Cancel Σ μ_i dn_i from both sides:

Σ n_i dμ_i = –S dT + V dP

Step 4: Constant temperature and pressure

For processes at constant T and P (dT = 0, dP = 0), we get:

Σ n_i dμ_i = 0

Step 5: Divide by total number of moles n = Σ n_i

Let x_i = n_i / n (mole frac on). Then:

Σ x_i dμ_i = 0

This is the Gibbs-Duhem equa on.

Significance:
It shows that the chemical poten als of components in a mixture cannot vary independently. If
one changes, others must adjust. It is fundamental to solu on thermodynamics, phase
equilibria, and colliga ve proper es.

iii) Derive the equa on for change in entropy of mixing of two ideal gases. [5]

Answer:

Consider: n₁ moles of ideal gas 1 and n₂ moles of ideal gas 2, ini ally separated by a par on at
temperature T and pressure P.
Ini al state:
Gas 1: volume V₁ = n₁RT/P
Gas 2: volume V₂ = n₂RT/P

Final state (a er removing par on):

Each gas occupies the total volume V = V₁ + V₂ = (n₁ + n₂)RT/P

Step 1: Entropy change for gas 1 (isothermal expansion from V₁ to V)

For isothermal expansion of an ideal gas:
ΔS₁ = n₁R ln(V/V₁) = n₁R ln[(V₁+V₂)/V₁]

But V₁ = x₁ V, where x₁ = n₁/(n₁+n₂)

Thus V/V₁ = 1/x₁, so ΔS₁ = n₁R ln(1/x₁) = – n₁R ln x₁

Step 2: Entropy change for gas 2

Similarly, ΔS₂ = n₂R ln(V/V₂) = n₂R ln(1/x₂) = – n₂R ln x₂

Step 3: Total entropy change

ΔS_mix = ΔS₁ + ΔS₂ = – n₁R ln x₁ – n₂R ln x₂

Step 4: For one mole of mixture

Let n = n₁ + n₂ = 1 mole. Then n₁ = x₁, n₂ = x₂, and

ΔS_mix = –R (x₁ ln x₁ + x₂ ln x₂)

Since x₁, x₂ < 1, ln x is nega ve, so ΔS_mix is posi ve, indica ng mixing is spontaneous.

Example: If n₁ = n₂ (x₁ = x₂ = 0.5),

ΔS_mix = –R[0.5 ln(0.5) + 0.5 ln(0.5)] = –R[0.5×(–0.693) + 0.5×(–0.693)] = –R[–0.693] = 0.693R =
5.76 J/K·mol.

Thus, entropy of mixing is a driving force for spontaneous mixing of ideal gases.

(Page 2 top) A empt any two of the following [4 marks, 2 marks each]

i) One mole of an ideal gas, maintained at 4.1 atm pressure and at a certain temperature,
absorbs heat 3710 J and expands to two litres. Calculate the entropy change in expansion
process. [2]

Answer:
Given:
n = 1 mol, P = 4.1 atm (constant pressure process? Or isothermal? Possibly isothermal
expansion.)

For an ideal gas undergoing isothermal reversible expansion, the entropy change is:

ΔS = q_rev / T

But T is not given directly. However, for an ideal gas at constant P,

q = ΔH = n Cp ΔT, but here expansion is at constant pressure? The wording "absorbs heat 3710 J
and expands to two litres" – likely means the gas expands from some ini al volume V₁ to V₂ = V₁
+ 2 L.

We need more data. If we assume the process is isothermal, then from first law for isothermal
ideal gas: q = W = nRT ln(V₂/V₁).

Without V₁ or T, we cannot get ΔS numerically. If the process is at constant pressure, then ΔS = n

Cp ln(T₂/T₁), but T₂ unknown.

Given the lack of data, the formula is:

For isothermal: ΔS = nR ln(V₂/V₁)
For constant P: ΔS = n Cp ln(T₂/T₁)

The ques on likely expects the expression, not a number.

ii) For the reac on Ag₂O(s) → 2Ag(s) + ½O₂(g), ΔH = 30.66 kJ mol⁻¹ and ΔS = 6.66 J K⁻¹ mol⁻¹ at
1 atm pressure. Calculate the temperature at which ΔG = 0. Also predict the direc on of the
reac on at this temperature and below this temperature. [2]

Answer:

Given:
ΔH = 30.66 kJ/mol = 30660 J/mol
ΔS = 6.66 J/K·mol

At equilibrium: ΔG = 0 = ΔH – TΔS

⇒ T = ΔH / ΔS = 30660 / 6.66 = 4604 K (approx.)

(Note: 6.66 J/K·mol is unusually small; possibly a typo – should be ~66.6 J/K·mol giving T ≈ 460
K.)

Direc on of reac on:

  ΔH > 0 (endothermic), ΔS > 0 (increase in disorder due to gas evolu on).

At T = 4604 K: ΔG = 0 → equilibrium.

Below T (T < 4604 K):

ΔG = ΔH – TΔS. Since ΔH > 0 and ΔS > 0, at low T the term –TΔS is small, so ΔG > 0 → reac on
is non-spontaneous in forward direc on (reverse reac on: decomposi on of Ag₂O? Wait,
forward is decomposi on, reverse is forma on of Ag₂O). So below T, forward reac on
(decomposi on) is non-spontaneous; the reverse (forma on of Ag₂O) is spontaneous.

Above T (T > 4604 K):

ΔG < 0 → forward reac on (decomposi on of Ag₂O) is spontaneous.

iii) Show that C_p – C_v = nR. [2]

Answer:

For an ideal gas:

From defini on:

C_p = (∂H/∂T)_P
C_v = (∂U/∂T)_V

Enthalpy H = U + PV

For an ideal gas, PV = nRT, so H = U + nRT

Differen ate with respect to T at constant P:

(∂H/∂T)_P = (∂U/∂T)_P + nR

But for an ideal gas, internal energy U depends only on temperature, so (∂U/∂T)_P = (∂U/∂T)_V
= C_v

Thus: C_p = C_v + nR

Hence: C_p – C_v = nR

Physical meaning: The difference is due to the work done by the gas when expanding against
constant pressure. For 1 mole, R ≈ 8.314 J/K·mol.

End of Sec on I – First Ques on Paper

PHYSICAL CHEMISTRY – SECOND QUESTION PAPER (PHYSICAL CHEMISTRY 2nd que [Link])

SECTION – I (COMPLETE)

Q1 a) Answer any four [8 marks, 2 marks each]

i) Classify the molecules on the basis of moments of iner a. CH₂=CH₂, O₃, SO₃ [2]

Answer:

Molecules are classified into four types based on the equality of their principal moments of
iner a (Iₐ, I_b, I_c).

1. Linear molecules:
Iₐ = 0, I_b = I_c
Example: OCS, CO₂, HCl

2. Spherical tops:
Iₐ = I_b = I_c
Example: CH₄, SF₆

3. Symmetric tops:
Two moments equal, third different.

 Prolate symmetric top (cigar shape): Iₐ < I_b = I_c

 Oblate symmetric top (disc shape): Iₐ = I_b < I_c

4. Asymmetric tops:
All three moments different.

Classifica on of given molecules:

Molecule Structure Moment of iner a type

CH₂=CH₂ (ethylene) Planar, H₂C=CH₂ Oblate symmetric top (Iₐ = I_b < I_c)

O₃ (ozone) Bent (non-linear) Asymmetric top (all I different)

Molecule Structure Moment of iner a type

SO₃ (sulfur trioxide) Trigonal planar Oblate symmetric top (Iₐ = I_b < I_c)

Note: O₃ is bent (~117°), so it is asymmetric. SO₃ is perfectly symmetric planar.

ii) Explain the term Hooke's law. [2]

Answer:

Hooke's law states that within the elas c limit, the restoring force (F) exerted by a spring or a
chemical bond is directly propor onal to the displacement (x) from its equilibrium posi on, and
opposite in direc on:

F = –k x

where:

 k = force constant (N/m or dyne/cm)

 x = displacement from equilibrium (m or cm)

Significance in vibra onal spectroscopy:

For a diatomic molecule treated as a harmonic oscillator, the vibra onal frequency is:

ν = (1/2π) √(k/μ)

where μ = reduced mass = m₁m₂/(m₁+m₂)

Implica ons:

 A stronger bond (larger k) gives higher vibra onal frequency.

 Isotopic subs tu on changes μ, affec ng ν (e.g., H–Cl vs D–Cl).

 Hooke's law is the basis for the harmonic oscillator model, which is a good
approxima on for low vibra onal levels.

 Anharmonicity (devia on from Hooke's law) occurs at higher energies, leading to

overtone bands and eventual bond dissocia on.

Example: For H–Cl, k ≈ 480 N/m, μ ≈ 0.97×10⁻²⁷ kg, giving ν ≈ 8.6×10¹³ Hz (2886 cm⁻¹).
iii) What do you mean by molecular polarizability? [2]

Answer:

Molecular polarizability (α) is a measure of the ease with which the electron cloud of a
molecule can be distorted by an external electric field.

When an external electric field E is applied, an induced dipole moment μ_ind is produced:

μ_ind = α E

where α is the polarizability tensor (scalar for isotropic molecules).

Units:
C·m²/V or ų (1 ų = 10⁻³⁰ m³). Typically α ~ 1–10 ų for small molecules.

Factors affec ng polarizability:

 Number of electrons: Larger molecules have higher α.

 Electron cloud distribu on: Delocalized electrons (π systems, aroma c) are more
polarizable.

 Bond type: Covalent bonds with mobile electrons (e.g., C–I) have higher α than C–H.

Importance in spectroscopy:

 Raman effect: The intensity of Raman sca ering depends on (∂α/∂q)². Vibra ons that
change polarizability are Raman ac ve.

 Refrac ve index: Related to polarizability via Lorentz-Lorenz equa on.

 Intermolecular forces: London dispersion forces arise from instantaneous induced

dipoles, propor onal to α².

Example: Benzene (α ≈ 10.3 ų) is more polarizable than hexane (α ≈ 11.8? Actually hexane
larger). He (α = 0.205 ų) is very low.

iv) Write down Born-Oppenheimer approxima on. [2]

Answer:

The Born-Oppenheimer approxima on (also called the adiaba c approxima on) is a

fundamental simplifica on in quantum chemistry. It states that because the nuclei are much
heavier (by a factor of ~10³–10⁴) than electrons, the mo on of electrons and nuclei can be
separated.
Mathema cal form:

Total wave func on: ψ_total(r, R) = ψ_electron(r; R) × ψ_nuclear(R)

where:

 r = electronic coordinates

 R = nuclear coordinates

Procedure:

1. For fixed nuclear posi ons R, solve the electronic Schrödinger equa on:
[Ĥ_electron + V_nn(R)] ψ_electron(r; R) = E_electron(R) ψ_electron(r; R)

2. The electronic energy E_electron(R) becomes the poten al energy for nuclear mo on.

3. Then solve the nuclear Schrödinger equa on:

[–(ħ²/2) Σ (1/M_i) ∇_i² + E_electron(R)] ψ_nuclear(R) = E_total ψ_nuclear(R)

Consequences:

 The poten al energy surface (PES) is defined.

 Vibra onal and rota onal mo ons are treated separately from electronic structure.

 Molecular geometry op miza on is possible.

Limita ons:
The approxima on fails when two electronic states become close in energy (non-adiaba c
effects, e.g., in photochemistry).

Importance: Without this approxima on, solving the full Schrödinger equa on for molecules
would be computa onally impossible.

v) Give the applica ons of Mössbauer spectroscopy. [2]

Answer:

Mössbauer spectroscopy is a powerful technique based on recoil-free resonant absorp on of

gamma rays. Its main applica ons include:

1. Oxida on state determina on (Isomer shi ):

 Example: ⁵⁷Fe: Fe²⁺ (high spin) → δ ~ 1.0–1.5 mm/s; Fe³⁺ → δ ~ 0.3–0.6 mm/s rela ve to
α-Fe.
  Used to iden fy iron in minerals (olivine, pyroxene), biological samples (hemoglobin,
ferredoxin), and catalysts.

2. Magne c proper es (Hyperfine spli ng):

 Below Néel temperature, magne c ordering produces a sextet (6 lines).

 Determines internal magne c fields at the nucleus.

 Used to study ferromagnets, an ferromagnets (e.g., Fe₃O₄, α-Fe₂O₃), and

superparamagne sm.

3. Phase iden fica on and quan fica on:

 Each iron-containing phase (e.g., FeO, Fe₂O₃, Fe₃O₄) has a dis nct Mössbauer fingerprint.

 Used in corrosion studies (rust analysis), archaeology (ancient pigments), and planetary
science (Mars meteorites).

4. Chemical environment (Quadrupole spli ng):

 Due to electric field gradient from asymmetric charge distribu on.

 Dis nguishes between high-spin and low-spin Fe, or between different coordina on
geometries.

5. Biological applica ons:

 Study of iron-sulfur proteins (rubredoxin, ferredoxin) and heme proteins (myoglobin,

cytochrome c).

6. Geology and mineralogy:

 Analysis of lunar samples and meteorites.

 Determining Fe oxida on state in mantle minerals.

7. Materials science:

 Study of magne c nanopar cles, ferrofluids, and amorphous alloys.

Thus, Mössbauer spectroscopy is uniquely sensi ve to the electronic and magne c environment
of specific nuclei (especially ⁵⁷Fe, ¹¹⁹Sn, ¹²¹Sb, ¹²⁵Te, ¹⁵¹Eu, ¹⁹⁷Au).

Q1 b) The spacing between the lines in the microwave spectrum of H³⁵Cl is 6.350 × 10¹¹ Hz.
Calculate the bond length of H³⁵Cl. [3]
Answer:

Given:
Spacing between adjacent rota onal lines = 6.350 × 10¹¹ Hz
Molecule: H³⁵Cl
h = 6.626×10⁻³⁴ J·s
c = 2.998×10¹⁰ cm/s
1 u = 1.6605×10⁻²⁷ kg

Step 1: Relate spacing to rota onal constant

For a rigid diatomic rotor, rota onal energy levels: E_J = J(J+1)hB (in J) or E_J = J(J+1)hcB (in
cm⁻¹).
The spacing between adjacent lines in a pure rota onal spectrum (J → J+1) is:

Δν = 2B (in Hz)
because the transi on frequency for J → J+1 is ν = 2B(J+1), so difference between successive J
values is 2B.

Thus: 2B = 6.350×10¹¹ Hz
B = 3.175×10¹¹ Hz

Step 2: Convert B to energy units

B (in J) = hB (in Hz) = 6.626×10⁻³⁴ × 3.175×10¹¹ = 2.104×10⁻²² J

Step 3: Relate B to moment of iner a

For a rigid rotor: B = h/(8π²I) (in Hz)
Thus I = h/(8π²B) = 6.626×10⁻³⁴ / (8 × 9.8696 × 3.175×10¹¹)

8π² = 78.9568
Denominator = 78.9568 × 3.175×10¹¹ = 2.507×10¹³

I = 6.626×10⁻³⁴ / 2.507×10¹³ = 2.643×10⁻⁴⁷ kg·m²

Step 4: Calculate reduced mass μ

Atomic masses: H = 1.0078 u, Cl = 34.9689 u

μ = (m_H × m_Cl) / (m_H + m_Cl) = (1.0078 × 34.9689) / (1.0078 + 34.9689)

Numerator = 35.242
Denominator = 35.9767
μ = 35.242 / 35.9767 = 0.9796 u

μ in kg = 0.9796 × 1.6605×10⁻²⁷ = 1.626×10⁻²⁷ kg

Step 5: Calculate bond length r
I = μ r² ⇒ r = √(I/μ) = √(2.643×10⁻⁴⁷ / 1.626×10⁻²⁷) = √(1.626×10⁻²⁰) = 1.275×10⁻¹⁰ m

r = 1.275 × 10⁻¹⁰ m = 1.275 Å

Thus the bond length of H³⁵Cl is 1.275 Å (which agrees with literature value).

Q2 a) A empt any three of the following [9 marks, 3 marks each]

i) Sketch and explain the different stretching vibra onal frequencies for CO₂ molecule. [3]

Answer:

CO₂ is a linear triatomic molecule (O=C=O). It has 4 normal modes of vibra on (3N – 5 for linear
= 4).

Mode 1: Symmetric stretch (ν₁)

 Both C=O bonds stretch and compress in phase.

 Dipole moment remains zero (symmetric).

 IR inac ve (no change in dipole moment).

 Raman ac ve (polarizability changes).

 Frequency: ν₁ ≈ 1340 cm⁻¹ (Raman).

Mode 2: Asymmetric stretch (ν₃)

 One bond stretches while the other compresses (out of phase).

 Dipole moment changes (oscillates).

 IR ac ve (strong band).

 Raman ac ve (weak).

 Frequency: ν₃ ≈ 2349 cm⁻¹ (IR strong).

Mode 3 & 4: Bending (degenerate) (ν₂)

 Two perpendicular bending modes (in-plane and out-of-plane) – degenerate (same

frequency).

 Molecule bends, O–C–O angle changes.

  Dipole moment changes.

 IR ac ve.

 Raman inac ve (no change in polarizability for this mode).

 Frequency: ν₂ ≈ 667 cm⁻¹ (IR).

Diagram descrip on:

text

Symmetric stretch: O=C=O → O=C=O

<--- ---> (in phase)

Asymmetric stretch: O=C=O → O←C→O

<--- ---> (out of phase)

Bending: O O

╲ ╱

╱ ╲

O O

Summary table:

Mode Type IR ac vity Raman ac vity Frequency (cm⁻¹)

ν₁ Symmetric stretch Inac ve Ac ve ~1340

ν₂ Bending (2×) Ac ve Inac ve ~667

ν₃ Asymmetric stretch Ac ve Weak ~2349

ii) Write a note on Birge-Sponer extrapola on plot. [3]

Answer:

The Birge-Sponer extrapola on is a graphical method used to determine the bond dissocia on
energy (D₀) of a diatomic molecule from vibra onal spectroscopy data.

Principle:
For a real (anharmonic) molecule, the energy spacing between successive vibra onal levels
decreases as v increases. The vibra onal term G(v) is given by:

G(v) = ωₑ(v + ½) – ωₑxₑ(v + ½)² + ...

The difference between adjacent levels is:

ΔG(v + ½) = G(v+1) – G(v) = ωₑ – 2ωₑxₑ(v + 1)

This is a linear func on of (v + 1).

Procedure:

1. From the infrared or Raman spectrum, measure the posi ons of vibra onal transi ons
(fundamental, first overtone, etc.).

2. Calculate ΔG(v + ½) for each available level.

3. Plot ΔG (in cm⁻¹) on the y-axis against (v + 1) on the x-axis.

4. Extrapolate the straight line to ΔG = 0. The x-intercept gives v_max (the highest
vibra onal level before dissocia on).

5. The bond dissocia on energy D₀ (from v = 0) is the area under the curve (or the sum of
all ΔG values from v = 0 to v_max).

Mathema cally:
D₀ = Σ_{v=0}^{v_max} ΔG(v + ½) ≈ (ωₑ²)/(4ωₑxₑ)

Example: For I₂, the Birge-Sponer plot gives D₀ ≈ 1.54 eV (literature value).

Limita ons:

 Requires data for many vibra onal levels.

 Extrapola on assumes linearity, which may fail near dissocia on.

 Modern methods use direct poten al fi ng (Rydberg-Klein-Rees).

iii) Discuss the classical method for Raman effect. [3]

Answer:

The classical theory of Raman sca ering explains the origin of Raman lines using the concept
of polarizability modula on by molecular vibra ons.

Step 1: Incident light induces a dipole moment

When a molecule is placed in an oscilla ng electric field E = E₀ cos(2πν₀ t), an induced dipole
moment is produced:

μ_ind = α E

where α is the molecular polarizability.

Step 2: Polarizability changes with vibra on

For a vibra ng molecule, the polarizability varies with the vibra onal coordinate q:

α = α₀ + (∂α/∂q)₀ q

If the vibra on is harmonic: q = q₀ cos(2πν_vib t)

Step 3: Subs tute into μ_ind

μ_ind = [α₀ + (∂α/∂q)₀ q₀ cos(2πν_vib t)] × E₀ cos(2πν₀ t)

= α₀E₀ cos(2πν₀ t) + ½ (∂α/∂q)₀ q₀ E₀ [cos{2π(ν₀ – ν_vib)t} + cos{2π(ν₀ + ν_vib)t}]

Step 4: Interpreta on of frequency components

Frequency component Type Condi on

ν₀ Rayleigh sca ering Always present

ν₀ – ν_vib Stokes Raman line ∂α/∂q ≠ 0

ν₀ + ν_vib An -Stokes Raman line ∂α/∂q ≠ 0

Selec on rule: A vibra on is Raman ac ve if ∂α/∂q ≠ 0 (polarizability changes during the

vibra on).

Comparison with IR:

IR ac vity requires change in permanent dipole moment (∂μ/∂q ≠ 0).
Thus, a mode can be IR ac ve but Raman inac ve, or vice versa (e.g., CO₂ symmetric stretch: IR
inac ve, Raman ac ve).

Limita ons of classical theory:

 Does not explain intensity ra os of Stokes vs An -Stokes lines (quantum theory does).

 Cannot explain the existence of rota onal Raman lines (requires quantum mechanics).

iv) Explain the principle of Mössbauer spectroscopy. [3]

Answer:

Principle:
Mössbauer spectroscopy is based on the recoil-free resonant absorp on of gamma rays by
nuclei bound in a solid la ce. It was discovered by Rudolf Mössbauer in 1957 (Nobel Prize).

Key concepts:

1. Nuclear resonance:

 A radioac ve source (e.g., ⁵⁷Co) decays to an excited state of ⁵⁷Fe, which emits a gamma
ray (14.4 keV).

 This gamma ray can be resonantly absorbed by ⁵⁷Fe nuclei in a sample if the energy
matches exactly.

 Normally, recoil of the nucleus during emission/absorp on shi s the energy away from
resonance.

2. Recoilless frac on:

 In a solid, nuclei are bound in a crystal la ce. For low-energy gamma rays, the en re
la ce can recoil as a whole (recoilless absorp on/emission).

 The recoilless frac on (f) depends on temperature and la ce s ffness. At low T, f is high.

3. Doppler modula on:

 To scan through resonance, the source is moved rela ve to the sample at velocity v.

 The gamma ray energy is Doppler-shi ed: E = E₀ (1 + v/c)

 By varying v (± few mm/s), a Mössbauer spectrum is obtained (counts vs velocity).

4. Parameters obtained:
Parameter Informa on obtained

Isomer shi (δ) Electron density at nucleus → oxida on state, covalency

Quadrupole spli ng (ΔE_Q) Electric field gradient → symmetry around nucleus

Magne c hyperfine spli ng Internal magne c field → magne c ordering

Typical setup:

 Source (e.g., ⁵⁷Co in Rh matrix)

 Absorber (sample)

 Mo on drive (Doppler velocity)

 Detector (propor onal counter)

 Mul channel analyzer

Applica ons: Iron-containing minerals, biological samples (hemoglobin), catalysts, magne c

materials, corrosion studies.

Q2 b) In the pure rota onal spectrum of XY molecule, the adjacent lines are separated by 8
cm⁻¹. If the molecule is irradiated by radia on of 20,000 cm⁻¹, what is the wave number of
first Stokes lines? [3]

Answer:

Given:
Spacing between adjacent rota onal lines = 8 cm⁻¹
For a pure rota onal spectrum (microwave), the spacing = 2B (where B is rota onal constant in
cm⁻¹).

Thus: 2B = 8 cm⁻¹ ⇒ B = 4 cm⁻¹

The molecule is irradiated by light of wavenumber ν₀ = 20,000 cm⁻¹ (visible/UV).

Rota onal Raman effect:

For a linear molecule, rota onal Raman transi ons obey ΔJ = 0, ±2.
First Stokes line corresponds to ΔJ = +2 (J = 0 → J = 2). The Raman shi (change in wavenumber)
is:

Δν̄ = B[ J(J+1) – J'(J'+1) ] but be er: For Stokes, ν̄_stokes = ν₀ – [B(4J+6)] for J → J+2.

For J=0 → J=2: Δν̄ = B[2×3 – 0×1] = 6B = 6 × 4 = 24 cm⁻¹

Thus ν̄_stokes = ν₀ – 24 = 20000 – 24 = 19976 cm⁻¹

Alterna vely:
The rota onal Raman shi formula for a linear rotor:
Stokes shi = 4B(J + 3/2)?? Let's use standard: Δν̄ = 4B(J + 3/2) for J → J+2? Check: For J=0, Δν̄ =
4B(1.5)=6B. Yes.

So first Stokes line (J=0) shi = 6B = 24 cm⁻¹.

Answer: 19976 cm⁻¹

Q3 a) A empt any two of the following [8 marks, 4 marks each]

i) What is the significance of zero point energy? Obtain an expression for zero point energy of
harmonic and anharmonic oscillator. [4]

Answer:

Zero point energy (ZPE) is the minimum energy that a quantum system can have at absolute
zero temperature. It arises from the Heisenberg uncertainty principle: a par cle cannot be
completely at rest because that would require knowing both its posi on and momentum
exactly.

Significance of ZPE:

1. Prevents molecular collapse: Without ZPE, molecules would freeze into a single lowest-
energy configura on; ZPE ensures atoms vibrate even at 0 K.

2. Isotope effects: Heavier isotopes have lower ZPE (ν ∝ 1/√μ). This affects reac on rates
(kine c isotope effect) and equilibrium constants.

3. Bond dissocia on energy: The true dissocia on energy D₀ = Dₑ – ZPE, where Dₑ is the
depth of the poten al well. D₀ is the experimentally measured bond dissocia on energy.

4. Phase transi ons: In helium, ZPE is large enough to prevent freezing at atmospheric
pressure (helium remains liquid down to ~0 K).
 5. Chemical reac ons: ZPE differences between reactants and products affect ac va on
energies.

Expression for harmonic oscillator:

Energy levels: E_v = (v + ½)hν, v = 0, 1, 2, ...
At v = 0: E₀ = ½hν (in J) or E₀ = ½hcν̄ (in cm⁻¹).

Expression for anharmonic oscillator (Morse poten al):

Energy levels: E_v = (v + ½)hνₑ – (v + ½)²hνₑ xₑ
At v = 0: E₀ = ½hνₑ – ¼hνₑ xₑ

where xₑ is the anharmonicity constant (dimensionless).

Since xₑ is posi ve (e.g., for H–Cl, xₑ ≈ 0.017), the anharmonic ZPE is slightly less than the
harmonic ZPE.

Numerical example for H–Cl:

ν̄ = 2886 cm⁻¹, xₑ = 0.017
Harmonic ZPE = ½ × 2886 = 1443 cm⁻¹
Anharmonic ZPE = ½×2886 – ¼×2886×0.017 = 1443 – 12.3 = 1430.7 cm⁻¹

Thus ZPE is a real, measurable quan ty with profound physical consequences.

ii) Discuss the Franck-Condon principle in electronic spectroscopy. [4]

Answer:

The Franck-Condon principle is a key concept in molecular spectroscopy that explains the
intensity distribu on of vibra onal bands in electronic spectra. It states that electronic
transi ons occur so rapidly (∼10⁻¹⁵ s) that the posi ons and momenta of the nuclei do not
change during the transi on. Thus, the transi on is represented by a ver cal line on a poten al
energy diagram.

Key points:

1. Ver cal transi ons:

The molecule jumps from the ground electronic state (with its equilibrium nuclear geometry) to
an excited electronic state, but the nuclei have no me to move. The transi on lands on the
poten al energy curve of the excited state at the same internuclear distance R.

2. Overlap integral (Franck-Condon factor):

The intensity of a vibronic transi on (v'' → v') is propor onal to the square of the overlap
integral between the vibra onal wave func ons of the two electronic states:
I ∝ |⟨ψ_v' | ψ_v''⟩|²

This is called the Franck-Condon factor.

3. Most probable transi on:

If the poten al energy curves of ground and excited states have the same equilibrium bond
length (Rₑ' = Rₑ''), the ver cal transi on from v''=0 goes to v'=0 (Δv = 0 – no vibra onal
progression).

If Rₑ' > Rₑ'' (bond length increases in excited state), the ver cal transi on from v''=0 goes to a
higher v' level (v' > 0). The Franck-Condon maximum occurs where the wave func ons overlap
best.

4. Diagram descrip on:

 x-axis: internuclear distance R

 y-axis: poten al energy

 Lower curve: ground state (S₀)

 Upper curve: excited state (S₁)

 Ver cal arrow from v''=0 to the turning point of the excited state

 The ver cal line hits the excited state curve at a higher v' level.

Example: Iodine molecule (I₂): The B³Π_u⁺ ← X¹Σ_g⁺ transi on shows a long progression of
vibra onal bands because the excited state has a much larger bond length. The Franck-Condon
maximum occurs at v' ≈ 20–30.

Consequences:

 The envelope of the vibra onal progression is determined by the displacement between
poten al curves.

 Short progressions → Rₑ' ≈ Rₑ''

 Long progressions → Rₑ' significantly different from Rₑ''

 Dissocia on can occur if the ver cal transi on goes above the dissocia on limit.

The Franck-Condon principle is essen al for interpre ng UV-Vis spectra of molecules and for
understanding photodissocia on dynamics.

iii) Discuss the rota onal fine structure of electronic vibra on transi ons. [4]
Answer:

In electronic spectra (UV-Vis), each vibra onal band is split into many closely spaced lines due
to simultaneous changes in rota onal quantum number. This is called rota onal fine structure.

Selec on rules for electronic transi ons:

For a diatomic molecule, the total angular momentum selec on rule is:

ΔJ = 0, ±1 (but J=0 → J=0 is forbidden for Σ–Σ transi ons)

Three branches:

Branch ΔJ Frequency (wavenumber)

P branch ΔJ = –1 (J → J–1) ν = ν₀ – 2B''J (J = 1, 2, ...)

Q branch ΔJ = 0 (J → J) ν = ν₀ (if B' = B'') or ν₀ + (B' – B'')J(J+1)

R branch ΔJ = +1 (J → J+1) ν = ν₀ + 2B'(J+1) (J = 0, 1, 2, ...)

where ν₀ is the band origin (pure electronic + vibra onal energy difference), B' and B'' are
rota onal constants in the excited and ground electronic states, respec vely.

Appearance of the spectrum:

 Q branch appears only if the electronic transi on involves a change in orbital angular
momentum (Λ ≠ 0) – e.g., Π–Σ, Δ–Π transi ons. For Σ–Σ transi ons, no Q branch.

 P and R branches are always present.

 Band head forma on: If B' < B'', the R branch lines converge to a maximum (band head)
and then fold back. If B' > B'', the P branch forms a band head.

Example:
For I₂ (B–X transi on), B' << B'', so the R branch forms a band head. The spectrum shows a
series of closely spaced lines, then a gap, then more lines.

Informa on obtained from rota onal fine structure:

 B' and B'' → bond lengths in ground and excited states.

 Centrifugal distor on constants.

 Λ-doubling (for Π states).

  Electronic symmetry (from presence/absence of Q branch).

For polyatomic molecules:

The rota onal structure is much more complex due to mul ple moments of iner a. However,
for linear and symmetric top molecules, similar branch structure appears.

Thus, rota onal fine structure is a powerful tool for determining molecular constants in excited
electronic states.

Q3 b) A empt any two of the following [4 marks, 2 marks each]

i) Calculate for a rigid diatomic molecule for which at 300 K, the rota onal constant is 1.56
cm⁻¹. [2]

(Assuming the ques on asks for J_max – the rota onal level with maximum popula on)

Answer:

Given: B = 1.56 cm⁻¹, T = 300 K

For a rigid diatomic rotor, the rela ve popula on of rota onal level J is:

N_J ∝ (2J+1) e^(–hcB J(J+1)/kT)

The most populated J (J_max) is found by se ng dN_J/dJ = 0, giving:

J_max = √(kT/(2hcB)) – ½

Constants:
k = 1.3806×10⁻²³ J/K
h = 6.626×10⁻³⁴ J·s
c = 2.998×10¹⁰ cm/s

hcB = 6.626×10⁻³⁴ × 2.998×10¹⁰ × 1.56 = 6.626×10⁻³⁴ × 4.677×10¹⁰ = 3.099×10⁻²³ J

kT = 1.3806×10⁻²³ × 300 = 4.142×10⁻²¹ J

kT/(2hcB) = 4.142×10⁻²¹ / (2 × 3.099×10⁻²³) = 4.142×10⁻²¹ / 6.198×10⁻²³ = 66.83

√66.83 = 8.175

J_max = 8.175 – 0.5 = 7.675 ≈ J = 8 (or 7, depending on rounding)

Thus the most populated rota onal level is around J = 8.

ii) The IR spectrum of a diatomic molecule exhibits transi ons at 2143.0 cm⁻¹ & 4260 cm⁻¹
corresponding excita ons from ground state to first and second vibra onal respec vely. What
is the value of fundamental frequency? [2]

Answer:

For an anharmonic oscillator:

E(v) = ωₑ(v + ½) – ωₑxₑ(v + ½)²

Transi on v=0 → v=1 (fundamental):

ΔE₁ = ωₑ – 2ωₑxₑ = 2143.0 cm⁻¹ …(1)

Transi on v=0 → v=2 (first overtone):

ΔE₂ = 2ωₑ – 6ωₑxₑ = 4260.0 cm⁻¹ …(2)

Mul ply equa on (1) by 2: 2ωₑ – 4ωₑxₑ = 4286.0 cm⁻¹

Subtract equa on (2): (2ωₑ – 4ωₑxₑ) – (2ωₑ – 6ωₑxₑ) = 4286.0 – 4260.0

2ωₑxₑ = 26 ⇒ ωₑxₑ = 13 cm⁻¹

From (1): ωₑ = 2143.0 + 2×13 = 2143 + 26 = 2169 cm⁻¹

Thus the fundamental frequency (ωₑ) = 2169 cm⁻¹

iii) If the vibra onal frequency of H₂ molecule is 4400 cm⁻¹, what will be the frequency of
HD? [2]

Answer:

Vibra onal frequency ν ∝ 1/√μ, where μ is reduced mass.

For H₂: μ_H₂ = (1 × 1)/(1 + 1) = 0.5 u

For HD: μ_HD = (1 × 2)/(1 + 2) = 2/3 = 0.66667 u

ν_HD / ν_H₂ = √(μ_H₂ / μ_HD) = √(0.5 / 0.66667) = √0.75 = 0.866025

ν_HD = 4400 × 0.866025 = 3810.5 cm⁻¹

Thus the vibra onal frequency of HD is approximately 3810 cm⁻¹.