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
Homework

The unperturbed wave functions for the infinite square well are .
Suppose we perturb the system by simply raising the “floor” of the well
a constant amount . Find the first-order correction to the energies.
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
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.
• 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 𝑒 𝑖 ( 𝜔 −𝜔 ) 𝑡 −1
𝑘𝑖 𝑘𝑖

𝑐 𝑘 ( 𝑡 )= ( + )
ℏ 𝜔 𝑘𝑖 +𝜔 𝜔𝑘𝑖 − 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

The Einstein Coefficients

Stimulated emission
Foundations of Chemical Spectroscopy

Atomic Spectra
Foundations of Chemical Spectroscopy

Pure Rotational Spectra of Molecules

Foundations of Chemical Spectroscopy

Vibrational-Rotational Spectra of Molecules

Foundations of Chemical Spectroscopy

Raman Spectra
Foundations of Chemical Spectroscopy

Electronic Spectra of Molecules