Physical Chemistry II

2024 Spring
Sep. 10
Chapter 13

Foundations of Chemical Spectroscopy

• Emission and Absorption Spectra
• Atomic Spectra
• Pure Rotational Spectra of Molecules
• Vibrational-Rotational Spectra of Molecules
• Raman Spectra
• Electronic Spectra of Molecules
Foundations of Chemical Spectroscopy

Emission and Absorption Spectra

Schematic of a simple double-beam
spectrophotometer
Dirac Notation
(11.13 Approximation Methods in Quantum Mechanics, p
569)

• The wave function is written in the bra and is written in the ket .

• In a complete set, , and (for k ≠ i).

Dirac Notation
(11.13 Approximation Methods in Quantum Mechanics, p
569)

• The observation, .

• The Hermitian property, is written .

• The projector is .
Time-independent Schrödinger equation

The typical stationary states arising from the

solution (eigenvalue or eigenstates) of the
time-independent Schrödinger equation.

^
𝐻 𝜓 𝑖 =𝐸 𝑖 𝜓 𝑖

^
𝐻 |𝜓 𝑖 ⟩ = 𝐸 𝑖| 𝜓 𝑖 ⟩
Perturbation theory
The idea is to start with a simple system for which a
mathematical solution is known, and add an additional
"perturbing" Hamiltonian representing a weak disturbance
perturbation to the system.

If the disturbance is not too large, the various physical

quantities associated with the perturbed system (e.g. its
energy levels and eigenstates) can be expressed as
"corrections" to those of the simple system.

Chemistry LibreTexts 1 Chemistry LibreTexts 2

Perturbation theory
Perturbated

^ ^ 0 ^ 1 ^ 2
𝐻 =𝐻 + 𝐻 + 𝐻 + ⋯
0 1 2
𝜓 𝑖=𝜓 +𝜓 +𝜓 + ⋯
𝑖 𝑖 𝑖

0 1 2
𝐸 𝑖 = 𝐸 + 𝐸 + 𝐸 +⋯
𝑖 𝑖 𝑖

Second-order correction
First-order correction
Unperturbated
Perturbation theory

Unperturbated Schrödinger Equation

𝐻 |𝜓 𝑖 ⟩ = 𝐸𝑖 |𝜓 𝑖 ⟩
^ 0 0 0 0

(first-order) Perturbated Schrödinger Equation

𝐻 )(| 𝜓 𝑖 ⟩ +|𝜓 𝑖 ⟩ )=( 𝐸𝑖 + 𝐸 𝑖 )(|𝜓 𝑖 ⟩ +|𝜓 𝑖 ⟩ )

^ +^
0 1 0 1 0 1 0 1
(𝐻
Physical Chemistry II
2024 Spring
Sep. 12
Perturbation theory

Perturbated Schrödinger Equation

𝐻 1)(| 𝜓 0𝑖 ⟩ +|𝜓 1𝑖 ⟩ )=( 𝐸𝑖0 + 𝐸 1𝑖 )(|𝜓 0𝑖 ⟩ +|𝜓 1𝑖 ⟩ )
^0+ ^
(𝐻

𝐻 0|𝜓 0𝑖 ⟩ + 𝐻
^ ^ 0|𝜓 1 ⟩ + ^
𝑖 𝐻 1|𝜓 0𝑖 ⟩ + ^
𝐻 1|𝜓 1𝑖 ⟩ = 𝐸 0𝑖 |𝜓 0𝑖 ⟩ + 𝐸0𝑖 |𝜓 1𝑖 ⟩ + 𝐸1𝑖 | 𝜓 0𝑖 ⟩ + 𝐸1𝑖 | 𝜓 1𝑖 ⟩

Unperturbated Schrödinger Equation Neglect the second order

⟹^
𝐻
0
| 𝑖
𝜓
1
⟩ + ^
𝐻
1
| 𝑖
𝜓
0
⟩ = 𝐸 𝑖|
0
𝜓
1
𝑖 ⟩ + 𝐸 𝑖|
1
𝜓 𝑖 ⟩
0
Perturbation theory 𝐻 |𝜓 𝑖 ⟩ + ^
^ 0 1
𝐻 |𝜓 𝑖 ⟩ = 𝐸𝑖 |𝜓 𝑖 ⟩ + 𝐸𝑖 |𝜓 𝑖 ⟩
1 0 0 1 1 0

× ⟨ 𝜓𝑖 |
0

⟨ 𝜓 0𝑖 |𝐻
^ 0|𝜓 1 ⟩ + ⟨ 𝜓 0|𝐻
𝑖 𝑖
^ 1|𝜓 0 ⟩ = ⟨ 𝜓 0|𝐸 0|𝜓 1 ⟩ + ⟨ 𝜓 0| 𝐸1|𝜓 0 ⟩
𝑖 𝑖 𝑖 𝑖 𝑖 𝑖 𝑖

R.H.S.
Orthonormal
Perturbation theory

⟨ 𝜓 0𝑖 |𝐻
^ 0|𝜓 1 ⟩ + ⟨ 𝜓 0|𝐻
𝑖 𝑖
^ 1|𝜓 0 ⟩ = ⟨ 𝜓 0|𝐸 0|𝜓 1 ⟩ + ⟨ 𝜓 0| 𝐸1|𝜓 0 ⟩
𝑖 𝑖 𝑖 𝑖 𝑖 𝑖 𝑖

L.H.S.

Hermitian
L.H.S.
Perturbation theory
⟨ 𝜓 |𝐻
^ |𝜓 ⟩ + ⟨ 𝜓 |𝐻
^ |𝜓 ⟩ = ⟨ 𝜓 |𝐸 |𝜓 ⟩ + ⟨ 𝜓 | 𝐸 |𝜓 ⟩
0
𝑖
0 1
𝑖
0
𝑖
1 0
𝑖
0
𝑖
0
𝑖
1
𝑖
0
𝑖
1
𝑖
0
𝑖

𝐸𝑖 ⟨ 𝜓 𝑖 |𝜓 𝑖 ⟩ + ⟨ 𝜓 𝑖 |𝐻
^ |𝜓 ⟩ = 𝐸 ⟨ 𝜓 |𝜓 ⟩ + 𝐸
0 0 1 0 1 0 0 0 1 1
𝑖 𝑖 𝑖 𝑖 𝑖

L.H.S. R.H.S.

𝐸𝑖 =⟨ 𝜓 𝑖 |𝐻
^ |𝜓 𝑖 ⟩
1 0 1 0
First-order corrected energy
Perturbation theory

Perturbated energy with

𝐸𝑖 = 𝐸 𝑖 + 𝐸𝑖 = 𝐸𝑖 + ⟨ 𝜓 𝑖 | ^
𝐻 |𝜓 𝑖 ⟩
0 1 0 0 1 0
first-order correction
Perturbation theory 𝐻 |𝜓 𝑖 ⟩ + ^
^ 0 1
𝐻 |𝜓 𝑖 ⟩ = 𝐸𝑖 |𝜓 𝑖 ⟩ + 𝐸𝑖 |𝜓 𝑖 ⟩
1 0 0 1 1 0

× ⟨ 𝜓 𝑘|
0
for k ≠ i

⟨ 𝜓 |𝐻
0
𝑘
^ |𝜓 ⟩ + ⟨ 𝜓 | ^
0 1
𝑖 𝐻 |𝜓 ⟩ = ⟨ 𝜓 | 𝐸 |𝜓 ⟩ + ⟨ 𝜓 |𝐸 |𝜓 ⟩
0
𝑘
1 0
𝑖
0
𝑘
0
𝑖
1
𝑖
0
𝑘
1
𝑖
0
𝑖

R.H.S.
Orthonormal
Perturbation theory

⟨ 𝜓 |𝐻
0
𝑘
^ |𝜓 ⟩ + ⟨ 𝜓 | ^
0 1
𝑖
0
𝑘𝐻 |𝜓 ⟩ = ⟨ 𝜓 | 𝐸 |𝜓 ⟩ + ⟨ 𝜓 |𝐸 |𝜓 ⟩
1 0
𝑖
0
𝑘
0
𝑖
1
𝑖
0
𝑘
1
𝑖
0
𝑖

L.H.S.
Hermitian
L.H.S.
Perturbation theory

⟨ 𝜓 |𝐻
0
𝑘
^ |𝜓 ⟩ + ⟨ 𝜓 | ^
0 1
𝑖 𝐻 |𝜓 ⟩ = ⟨ 𝜓 | 𝐸 |𝜓 ⟩ + ⟨ 𝜓 |𝐸 |𝜓 ⟩
0
𝑘
1 0
𝑖
0
𝑘
0
𝑖
1
𝑖
0
𝑘
1
𝑖
0
𝑖

𝐸 𝑘 ⟨ 𝜓 𝑘|𝜓 𝑖 ⟩ + ⟨ 𝜓 𝑘| ^
𝐻 |𝜓 𝑖 ⟩ = 𝐸𝑖 ⟨ 𝜓 𝑘|𝜓 𝑖 ⟩
0 0 1 0 1 0 0 0 1

L.H.S. R.H.S.

⟨ 𝜓 |
0 ^1
𝐻 |𝜓 𝑖⟩
0

⟨ 𝜓 𝑘|𝜓 𝑖 ⟩ = 𝐸 0 − 𝐸0 =𝑐𝑘𝑖
0 1 𝑘
is the weighting of to consist .
𝑖 𝑘

|𝜓 ⟩ ⟨ 𝜓 |𝜓 ⟩ = 𝑐 |𝜓 ⟩
0
𝑘
0
𝑘
1
𝑖 𝑘𝑖
0
𝑘
 ⟨ 𝜓 |
0 ^1
𝐻 |𝜓 𝑖⟩
0

Perturbation theory ⟨ 𝜓 𝑘|𝜓 𝑖 ⟩ = 𝐸 0 − 𝐸0 =𝑐𝑘𝑖

0 1 𝑘

𝑖 𝑘

Considering all the possible state j

|𝜓 ⟩ ⟨ 𝜓 |𝐻 |𝜓𝑖 ⟩
0 ^ 0
1 0
First-order corrected
|𝜓 ⟩ =∑
1
𝑖
𝑘 ≠𝑖
𝑘
0
𝐸 −𝐸
𝑘
0
=∑ 𝑐𝑘 𝑖|𝜓
𝑘 ≠𝑖
0
𝑘 ⟩ wavefunction
𝑖 𝑘
Perturbation theory

Perturbated energy with

𝐸𝑖 = 𝐸 𝑖 + 𝐸𝑖 = 𝐸𝑖 + ⟨ 𝜓 𝑖 | ^
𝐻 |𝜓 𝑖 ⟩
0 1 0 0 1 0
first-order correction

|𝜓 𝑖 ⟩ =|𝜓 ⟩ +|𝜓 ⟩ =|𝜓 ⟩ +∑ 𝑐 𝑘𝑖|𝜓 ⟩

0
𝑖
1
𝑖
0
𝑖
0
Perturbated wavefunction with
𝑘 first-order correction
𝑘≠ 𝑖

𝑐 𝑘𝑖=
⟨𝜓 𝑘|𝐻
0 ^ |𝜓 ⟩
1
𝑖
0

𝐸 0𝑖 − 𝐸0𝑘
Physical Chemistry II
2024 Spring
Sep. 19
Time-dependent wavefunction
For state i
− 𝑖 𝐸 𝑖 𝑡 /ℏ
Ψ 𝑖 ( 𝑥 , 𝑦 , 𝑧 , 𝑡 ) =𝜓 𝑖 ( 𝑥 , 𝑦 , 𝑧 ) 𝑒

|Ψ 𝑖 (𝑡 ) ⟩ =𝑒 |𝜓 𝑖 ⟩
−𝑖 𝐸 𝑖𝑡 /ℏ

Time dependent Time independent

t=0

|Ψ ⟩ =∑ 𝑐 𝑖 (𝑡)|Ψ (𝑡) ⟩ 0
𝑖 |Ψ 0
𝑖 (𝑡 ) ⟩ = 𝑒 | 𝜓𝑖 ⟩
− 𝑖𝐸𝑖𝑡/ ℏ

𝑖
Time-dependent Schrödinger equation
For state i
− 𝑖 𝐸 𝑖 𝑡 /ℏ
Ψ 𝑖 ( 𝑥 , 𝑦 , 𝑧 , 𝑡 ) =𝜓 𝑖 ( 𝑥 , 𝑦 , 𝑧 ) 𝑒

|Ψ 𝑖 (𝑡 ) ⟩ =𝑒 |𝜓 𝑖 ⟩
−𝑖 𝐸 𝑖𝑡 /ℏ

Time dependent Time independent

𝜕|Ψ 𝑖 (𝑡 ) ⟩ ^
iℏ =^
𝐻 |Ψ 𝑖 (𝑡 ) ⟩ 𝐻 |𝜓 𝑖 ⟩ = 𝐸 𝑖| 𝜓 𝑖 ⟩
𝜕𝑡
 𝜕|Ψ 𝑖 (𝑡 ) ⟩
iℏ =^
𝐻 |Ψ 𝑖 (𝑡 ) ⟩
Time-dependent Perturbation theory 𝜕 𝑡

𝜕|Ψ (𝑡) ⟩ 𝜕
[ 𝐻 + 𝐻 ( 𝑡 ) ]|Ψ (𝑡 )⟩ =i ℏ 𝜕 𝑡 =i ℏ 𝜕 𝑡 ∑ 𝑐𝑖 (𝑡 )|Ψ 𝑖 (𝑡 ) ⟩
^ ^ ′ 0

𝑑 𝑐 (𝑡) 𝑑|Ψ 0
(𝑡) ⟩
[𝐻^+^ 𝐻 ( 𝑡 ) ]|Ψ (𝑡) ⟩ =i ℏ ∑ |Ψ 𝑖 (𝑡) ⟩
′ 0
𝑑𝑡
𝑖
+i ℏ ∑ 𝑐 𝑖 (𝑡)
𝑖

𝑑𝑡
𝑖 𝑖
𝑑 𝑐𝑖 (𝑡)
[ 𝐻 + 𝐻 ( 𝑡 ) ]|Ψ (𝑡)⟩ =i ℏ∑ |Ψ 𝑖 (𝑡)⟩ 𝑑 𝑡 +∑ 𝑐 𝑖 (𝑡) 𝐻|Ψ 𝑖 (𝑡) ⟩
^ ^ ′ 0 ^ 0

𝑖 𝑖
𝑑 𝑐𝑖 (𝑡) ^
[ 𝐻 + 𝐻 ( 𝑡 ) ]|Ψ (𝑡)⟩ =i ℏ∑ |Ψ 𝑖 (𝑡)⟩ 𝑑 𝑡 + 𝐻 |Ψ ⟩
^ ^ ′ 0

𝑖
cancelled
 𝑑 𝑐𝑖 (𝑡)
^ 𝑡 )|Ψ (𝑡) ⟩ =i ℏ ∑ |Ψ 𝑖 (𝑡) ⟩
′ 0
Time-dependent Perturbation
𝐻 (theory
𝑑𝑡
𝑖

𝑑 𝑐 𝑖 (𝑡)
𝐻 (𝑡 ) ∑ 𝑐 𝑖 (𝑡)|Ψ 𝑖 (𝑡 ) ⟩ =iℏ ∑ |Ψ 𝑖 (𝑡) ⟩
^ ′ 0 0

𝑖 𝑖 𝑑𝑡

× ⟨ Ψ 𝑘 (𝑡 )|
0

𝑑 𝑐 𝑖 (𝑡) 𝑑 𝑐 𝑘 (𝑡)
∑ 𝑐𝑖 (𝑡) ⟨ Ψ (𝑡)|𝐻 ( 𝑡 )|Ψ 𝑖 (𝑡)⟩ =i ℏ ⟨ Ψ 𝑘 (𝑡)|∑ |Ψ 𝑖 (𝑡) ⟩ 𝑑𝑡 =i ℏ 𝑑𝑡
0
𝑘
^ ′ 0 0 0

𝑖 𝑖
Only i = k survives

𝑑 𝑐𝑘 (𝑡) 𝑖
=− ∑ 𝑐 𝑖 (𝑡) ⟨ Ψ 𝑘 (𝑡)|𝐻 ( 𝑡 )|Ψ 𝑖 (𝑡) ⟩
^
0 ′ 0
𝑑𝑡 ℏ 𝑖
 𝑑 𝑐𝑘 (𝑡) 𝑖
=− ∑ 𝑐 𝑖 (𝑡) ⟨ Ψ 0𝑘 (𝑡)|𝐻
^ ′ ( 𝑡 )|Ψ 0 (𝑡) ⟩
𝑖
𝑑𝑡 ℏ 𝑖
Time-dependent Perturbation
|Ψ theory
(𝑡 ) ⟩ = 𝑒 |𝜓 ⟩ 0
𝑖
− 𝑖𝐸𝑖𝑡/ ℏ
𝑖

Assuming there are only states and , and at , and .

𝑑 𝑐𝑘 (𝑡 ) 𝑖
=− [𝑐 𝑖 ( 𝑡 ) ⟨ Ψ 𝑘 ( 𝑡 )| ^
𝐻 ( 𝑡 )|Ψ 𝑖 ( 𝑡 ) ⟩ +𝑐 𝑘 (𝑡 ) ⟨ Ψ 𝑘 (𝑡 )|𝐻
^ ′ ( 𝑡 )|Ψ 0 (𝑡 ) ⟩ ]
0 ′ 0 0
𝑘
𝑑𝑡 ℏ

𝑑 𝑐𝑘 (𝑡 ) 𝑖 𝑖
=− ⟨ Ψ 𝑘 ( 𝑡 )| ^
𝐻 ( 𝑡 )|Ψ 𝑖 ( 𝑡 ) ⟩ =− ⟨ 𝜓 𝑘|𝑒 ^ |𝜓 𝑖 ⟩
0 ′ 0 𝑖𝐸 𝑡 /ℏ ′ − 𝑖𝐸 𝑡/ℏ
𝑘
𝐻 (𝑡) 𝑒 𝑖

𝑑𝑡 ℏ ℏ

𝑑 𝑐𝑘 (𝑡 ) 𝑖 𝑖 (𝐸
𝑑𝑡
=− 𝑒
ℏ
𝑘 − 𝐸𝑖 )𝑡 /ℏ
⟨ 𝜓𝑘|𝐻
^ ( 𝑡 )|𝜓 ⟩
′
𝑖
Physical Chemistry II
2024 Spring
Sep. 24
Perturbation from EM radiation

The EM waves perturbation the

population of states i and k.

𝑑 𝑐𝑘 (𝑡 ) 𝑖 𝑖 (𝐸
𝑑𝑡
=− 𝑒
ℏ
𝑘 − 𝐸𝑖 )𝑡 /ℏ
⟨ 𝜓𝑘|𝐻
^ ( 𝑡 )|𝜓 ⟩
′
𝑖
EM waves

°
𝐸 𝑥 ( 𝜔 , 𝑡 ) =2 𝐸𝑥 cos 𝜔 𝑡
The factor 2 is implemented for the
° future convivence.
𝐻 𝑥 ( 𝜔 ,𝑡 )=2 𝐻 𝑥 cos 𝜔 𝑡

• The EM waves are characterized by (in Hz or s-1) or (m).

• However, the number is too large using frequency (i.e., ).
• Wavenumber, , (in m-1 or cm-1) is usually utilized to represent
frequency.
• 1 cm-1 = 100 m-1
Interaction with EM waves

𝜇 𝑥 =𝑥 𝛿 𝑞 Electric dipole moment

• : distance
• : the separation of the electric charge

^ ′
^ 𝑥 𝐸 0𝑥 cos 𝜔 𝑡
𝐻 (𝑡 )=2 𝜇 Perturbating Hamiltonian from EM waves
Perturbation from EM radiation

𝑑 𝑐𝑘 (𝑡 ) 𝑖 𝑖 (𝐸
𝑑𝑡
=− 𝑒
ℏ
𝑘 − 𝐸𝑖 )𝑡 /ℏ
⟨ 𝜓 |𝐻
𝑘
^ ( 𝑡 )|𝜓 ⟩
′
𝑖

^ ′
^ 𝑥 𝐸 0𝑥 cos 𝜔 𝑡
𝐻 (𝑡 )=2 𝜇

The probability to find electron in state k

is .
 𝑑 𝑐𝑘 (𝑡 ) 𝑖 𝑖 (𝐸
Perturbation from EM radiation
𝑑𝑡
=− 𝑒
ℏ
𝑘 − 𝐸𝑖 )𝑡 /ℏ
⟨ 𝜓𝑘|𝐻
^ ( 𝑡 )|𝜓 ⟩
′
𝑖

^ ′
^ 𝑥 𝐸 0𝑥 cos 𝜔 𝑡
𝐻 (𝑡 )=2 𝜇

( 𝐸 𝑘 − 𝐸 𝑖) 𝑡
𝑑 𝑐𝑘 (𝑡 ) 𝑖 𝑖 ^ ′ ( 𝑡 )|𝜓 ⟩ =− 𝑖 𝑓 (𝜔 ,𝑡 ) 𝐸0 ⟨ 𝜓 |𝜇
𝑑𝑡
=− 𝑒
ℏ
ℏ
⟨𝜓 𝑘|𝐻 𝑖
ℏ 𝑖𝑘 𝑥 𝑘
^ 𝑥|𝜓 𝑖 ⟩

must be non-zero for i ≠ k to vary , known as allowed transition. When is zero,

the transition is forbidden.
 𝑑 𝑐𝑘 (𝑡 ) 𝑖
=− 𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) 𝐸 𝑥 ⟨ 𝜓 𝑘|𝜇
^ 𝑥|𝜓 𝑖 ⟩
0
Perturbation from EM radiation
𝑑𝑡 ℏ

Assuming

𝑑 𝑐𝑘 (𝑡 ) 𝑖 0
=− 𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) 𝐸 𝑥
𝑑𝑡 ℏ

( 𝐸 𝑘 − 𝐸𝑖 ) 𝑡 ( 𝐸𝑘 − 𝐸𝑖 ) 𝑡
𝑖 𝑖
ℏ ℏ 𝑖𝜔 𝑡 −𝑖 𝜔 𝑡
𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) =𝑒 ∙ 2 cos 𝜔 𝑡 = 𝑒 ∙(𝑒 +𝑒 )

( 𝐸 𝑘 − 𝐸 𝑖) 𝑡 ( 𝐸 𝑘 − 𝐸 𝑖) 𝑡
𝑖( +𝜔𝑡) 𝑖( −𝜔 𝑡 )
ℏ ℏ
𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) =𝑒 +𝑒
( 𝐸𝑘 − 𝐸𝑖 )
𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) =𝑒
𝑖 ( 𝜔𝑘𝑖 +𝜔 ) 𝑡
+𝑒
𝑖 ( 𝜔𝑘𝑖 − 𝜔 ) 𝑡 𝜔 𝑘𝑖 =
ℏ
 𝑑 𝑐𝑘 (𝑡 ) 𝑖 0
=− 𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) 𝐸 𝑥
𝑑𝑡 ℏ
Perturbation from EM radiation
𝑖 ( 𝜔𝑘𝑖 +𝜔 ) 𝑡 𝑖 ( 𝜔𝑘𝑖 − 𝜔 ) 𝑡
𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) =𝑒 +𝑒

𝑡
𝑖 0 𝑒( )
−1 𝑒 ( )
𝑖 𝜔𝑘𝑖 +𝜔 𝑡 𝑖 𝜔𝑘𝑖 −𝜔 𝑡
𝑖 0 −1
𝑐 𝑘 ( 𝑡 )=− 𝐸 𝑥 ∫ 𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) 𝑑𝑡=− 𝐸 𝑥 ( + )
ℏ 0 ℏ 𝑖 ( 𝜔𝑘𝑖 + 𝜔 ) 𝑖 ( 𝜔 𝑘𝑖 − 𝜔 )
0
𝐸 𝑥 𝑒 𝑖 ( 𝜔 + 𝜔 ) 𝑡 −1 𝑒𝑖 ( 𝜔 − 𝜔 )𝑡 − 1
𝑘𝑖 𝑘𝑖

𝑐 𝑘 ( 𝑡 )=− ( + )
ℏ 𝜔𝑘𝑖 + 𝜔 𝜔 𝑘𝑖 − 𝜔

Bohr Condition
• When 0, the second term is relevant, suggesting , known as stimulated
absorption.
• When 0, the first term is relevant, suggesting , known as stimulated
emission.
 𝑑 𝑐𝑘 (𝑡 ) 𝑖
Perturbation from EM radiation
𝑑𝑡
=− 𝑓 𝑖𝑘 ( 𝜔 , 𝑡 ) 𝐸 𝑥 ⟨ 𝜓 𝑘|𝜇
ℏ
0
^ 𝑥|𝜓 𝑖 ⟩

The spectral transitions are usually observed under the Bohr condition.
Therefore, we only need to focus on the selection rule( ).

The transition probability to state k under Bohr condition is

1 2
∗
𝑐 𝑘 ( 𝑡 ) 𝑐 𝑘 ( 𝑡 )= 2
[ ⟨ 𝜓 𝑘|𝜇^ 𝑥|𝜓 𝑖 ⟩ ] 𝐸
02
𝑥 𝑡
ℏ
The Einstein Coefficients

Stimulated
absorption

Spontaneous
emission Stimulated emission
 1 2
𝑐 ( 𝑡 ) 𝑐 𝑘 ( 𝑡 )= 2 [ ⟨ 𝜓 𝑘|𝜇𝑥|𝜓 𝑖 ⟩ ] 𝐸 𝑥 𝑡
∗
𝑘
^ 02

ℏ
The Einstein Coefficients
(Assuming the Bohr condition is fulfilled)

Stimulated i -> k
absorption ∗
𝑐 𝑘 ( 𝑡 ) 𝑐 𝑘 ( 𝑡 )= 𝐵𝑖𝑘 𝜌 ( 𝜔𝑘𝑖 )𝑡

2
2 𝜋 [ ⟨ 𝜓 𝑘|𝜇
^ 𝑥|𝜓 𝑖 ⟩ ]
𝐵𝑖𝑘= 2
= 𝐵 𝑘𝑖
3ℏ

: Einstein coefficient of stimulation absorption

: Einstein coefficient of stimulation emission
The Einstein Coefficients

If the number of particles in state i at time t = 0 is Ni, then the rate of transition to
state k of higher energy is

𝑑 𝑁𝑖
=− 𝑁 𝑖 𝐵𝑖 𝑘 𝜌 ( 𝜔𝑘 𝑖 )
𝑑𝑡

The rate of transition from state k of higher energy to state i is

𝑑 𝑁𝑘
=− 𝑁 𝑘 [ 𝐴 𝑘𝑖+ 𝐵𝑘𝑖 𝜌 (𝜔 𝑘𝑖 )]
𝑑𝑡

: Einstein coefficient of spontaneous emission

 𝑁𝑘 − Δ 𝐸/ 𝑘 𝑇
=𝑒 𝐵
Boltzmann distribution
𝑁𝑖
The Einstein Coefficients
3
h 𝜔𝑘𝑖 1
𝜌 ( 𝜔𝑘 𝑖 ) = 2 3
∙ −ℏ 𝜔𝑘𝑖 / 𝑘 𝐵 𝑇 Planck’s distribution
At equilibrium, 𝜋 𝑐 𝑒 −1

𝑑 𝑁 𝑖 𝑑 𝑁𝑘
= ⟹ − 𝑁 𝑖 𝐵𝑖 𝑘 𝜌 ( 𝜔 𝑘𝑖 )=− 𝑁 𝑘 [ 𝐴 𝑘𝑖 + 𝐵𝑘𝑖 𝜌 ( 𝜔 𝑘𝑖)]
𝑑𝑡 𝑑𝑡

𝑁𝑘 𝐵𝑘𝑖 𝜌 ( 𝜔 𝑘𝑖 ) −ℏ 𝜔 / 𝑘𝐵 𝑇
= =𝑒 𝑘𝑖

𝑁𝑖 𝐴 𝑘𝑖 + 𝐵𝑘𝑖 𝜌 ( 𝜔𝑘𝑖 )

3
𝐴𝑘𝑖 8 𝜋 h 𝜈𝑘𝑖
=
𝐵𝑘𝑖 𝑐
Foundations of Chemical Spectroscopy

Atomic Spectra
Atomic spectra

• Ranging from UV to IR
• The causes of spectral splitting
• Coulombic interactions
• Exchange interactions
• Spin-orbital interactions
Coulombic Interaction and Term Symbols

• Coulombic interaction results in the energy difference of the same

principal quantum number (e.g. 2s and 2p).
• To take account of the effect of Coulombic interactions, the atomic
energy levels are described by capital letters, called term symbols,
which indicate the magnitude of L, the total angular momentum.
𝐿= √ 𝑙 (𝑙+1) ℏ For single electron

𝑳=∑ 𝒍𝑖 =√ 𝐿(𝐿+1)ℏ For more than one electron

Coulombic Interaction and Term Symbols

• For the coupled angular momenta ( and ) can result in a total angular
moment , with the constraint
1. is an integer

• , the corresponding term symbols are S, P, D, F, …

Vector representation based on the angular
momentum
Assuming and representing to the electrons in 2p and 3p, respectively.
Vector representation based on the
quantum number
Assuming and representing to the electrons in 2p and 3p, respectively.
Exchange Interaction: Multiplicity of States

• Pauli principle
• Hund’s Rule

• Multiplicity
• 2S+1L
Exchange Interaction: Multiplicity ofMultiplicity
States
1 spin
Exchange Interaction: Multiplicity ofMultiplicity
States
2 spins

+ 𝛼 ( 1 ) 𝛽 ( 2 ) − 𝛼 ( 2 ) 𝛽 ( 1 ) ,𝑚 𝑠 1 +𝑚 𝑠 2=0
Exchange Interaction: Multiplicity of States
3 spins
Considering exciting helium J is the Coulombic integral.
K is the exchange integral.
(1s2 -> 1s12s1 or 1s12p1)

21P 23P
J+K
J-K
Spin-Orbit Interactions

• 2S+1LJ
 High-resolution spectroscopy

Spin-Orbit Interactions

Low-resolution spectroscopy
Spin-Orbit Interactions
(For hydrogen)

• 2S+1LJ

• Selection rules
Russell-Saunders Coupling
 • Total orbital angular momentum quantum number
Term symbols 2S+1
LJ • Multiplicity
• Total angular momentum quantum number

• L is non-negative.
• The maximum value, , of L is obtained when the total orbital angular
momenta are in the same direction.
• The minimum value, , of L is obtained when the total orbital angular
momenta are in the opposite direction.
• L: 0 1 2 3 4 5 6
• L: S P D F G H I
• The magnitude:
 • Total orbital angular momentum quantum number
Term symbols 2S+1
LJ • Multiplicity
• Total angular momentum quantum number

• For d2 ():

• For p3 (): :
 • Total orbital angular momentum quantum number
Term symbols 2S+1
LJ • Multiplicity
• Total angular momentum quantum number

• S is non-negative.
• Multiplicity
• The magnitude:

• , multiplicity = 1, singlet (e.g. 1s2, 2 paired electrons)

• , multiplicity = 2, doublet (e.g. 2s1, a lone electron)
• , multiplicity = 3, triplet (e.g. 2s12p1, 2 unpaired electrons)
 • Total orbital angular momentum quantum number
Term symbols 2S+1
LJ • Multiplicity
• Total angular momentum quantum number

• J is non-negative.
• The magnitude:
 • Total orbital angular momentum quantum number
Term symbols 2S+1
LJ • Multiplicity
• Total angular momentum quantum number

• For [He]2p13p1 (weak coupling, Russell-Saunders coupling, low Z):

L = 2, 1, 0
S = 1, 0
=> 1S, 3S, 1P, 3P, 1D, 3D

Considering J
1
S => 1S0 3
S => 3S1
1
P => 1P1 3
P => 3P2, 3P1, 3P0
1
D => 1D2 3
D => 3D3, 3D2, 3D1
 • Total orbital angular momentum quantum number
Term symbols 2S+1
LJ • Multiplicity
• Total angular momentum quantum number

• For p2 (strong coupling, jj-coupling, high Z):

Foundations of Chemical Spectroscopy

Pure Rotational Spectra of Molecules

 Types of Optical Spectra
Approximate Range
Spectroscopic Frequency Wavenumber Energy Types of Molecular Information
Region (s−1) (cm−1) (kJ mol−1) Energy Obtained
Interatomic
Microwave and far
109 – 1012 0.03 – 30 4×10−4 – 0.4 Rotation distance and
infrared
rotational constants
Interatomic
Vibration and
Infrared 1012 – 1014 30 – 3,000 0.4 – 40 distance and force
rotation
constants of bonds
Electronic energy
levels, bond
Electronic, dissociation
Visible and
10 – 10
14 16
3×10 – 3×10
3 5
40 – 4,000 vibration, and energies, force
ultraviolet
rotation constants of bonds,
and interatomic
distances
Typical energy separations for rotational,
vibrational, electronic levels
• When we try to solve the exact
Schrödinger equation, which takes into
account different forms of energy, the
energy cannot be separated into
rotational, vibrational, and electronic
contributions.
• With Born-Oppenheimer
approximation, the total energy E is the
sum of the electronic energy Ee, the
vibrational energy E𝜈, and the rotational
energy Er.
Typical energy separations for rotational,
vibrational, electronic levels
• This means, for example, that in dealing
with electronic energy of a diatomic
molecule we can take the distance
between the nuclei to be the
equilibrium distance, as if the molecule
were not vibrating.
• Similarly, in dealing with rotations we
can consider only the equilibrium
internuclear distances when we
calculate moments of inertia.
Typical energy separations for rotational,
vibrational, electronic levels
• If we make spectroscopic observations in the microwave and far-infrared regions, the only
transitions that occur are in the rotational state of the molecule. Pure rotational spectra observed
in those regions of the spectrum are therefore relatively simple.
• If we work in the near infrared, vibrational transitions occur and rotational transitions are
superimposed since there is ample energy to bring these about; a near-infrared spectrum is
therefore a vibrational-rotational spectrum also called ro-vibrational spectrum, and is a good deal
more complicated than a pure rotational spectrum.
• In the visible and ultraviolet regions electronic transitions occur, and at the same time there are
rotational and vibrational transitions. Electronic spectra are therefore even more complex than
the vibrational-rotational spectra.
Condition for Rotational Spectrum

• These involve transitions between different rotational states, but there is an important restriction;
rotational transitions are only observed in the spectrum if the molecule has a permanent dipole
moment.
• The reason for this is that the rotational motion must involve an oscillating dipole, which can
interact with an electromagnetic field; otherwise there can be no absorption or emission of
radiation.
• This means, as far as linear molecules are concerned, that molecules with a center of symmetry
(D∞h), such as N2 and C2H2 do not have a pure rotational spectrum, whereas those without a
center of symmetry (C ∞v), such as HF and HCN, do have a pure rotational spectrum.
Diatomic Molecules

• The rotational spectrum of a diatomic molecule can be treated by considering

the molecule to be a rigid rotor.
• The solution of the Schrödinger equation for this problem (rigid linear rotor,
11.10) shows that the magnitude of the angular momentum vector is given by
the equation

• where is the rotational quantum number. The energy in this approximation is

given by

• where is the moment of inertia and can have the values 0, 1, 2, …

Diatomic Molecules

• The eigenfunctions for the rotation of diatomic molecules are the spherical
harmonics (eq. 11.189), and therefore the quantum numbers that describe a
diatomic molecule are and .
(eq. 11.189)
• Each rotational level with quantum number has a degeneracy which arises in
the same way that the , values come from the degeneracy of the states in the
hydrogen atom.
Diatomic Molecules

• The angular momentum vector along the Z axis has 2J + 1 different values
according to its orientation in space with respect to a fixed axis.
• Each of the states has the same energy, and all are equally probable. A
statistical weighting factor of 2J + 1 is therefore assigned to each rotational
level.
• The relative population of states depends on this statistical factor and also on
the Boltzmann factor, , according to which the probability decreases as the
energy increases.
• The combination of these two factors causes the population and hence
intensity of the rotational states to in. crease initially and then decrease as the
energy increases.
 ( )
1
𝑘𝑇 1
𝐽 𝑚𝑎𝑥 ≈ 2
~ −2
Diatomic Molecules 2 h𝑐 𝐵

𝑔 𝐽 =( 2 𝐽 +1 ) 𝑒
−∆ 𝐸 𝑟𝑜𝑡 / 𝑘𝑇
Foundations of Chemical Spectroscopy

Vibrational-Rotational Spectra of Molecules

Foundations of Chemical Spectroscopy

Raman Spectra
Foundations of Chemical Spectroscopy

Electronic Spectra of Molecules