Chapter 1.

Review of QM Background
(1) Spectroscopy ; Experimental investigation

→ Energy levels of atoms or molecules

→ Absorption, emission, or scattering of e.m. radiation

by atoms or molecules are not continuous

Lyman series (nf = 1), ultraviolet

Balmer series (nf = 2), visible

Emission spectrum (in visible region)

of hydrogen atom

Paschen series (nf = 3), infrared

(2) Quantum Mechanics ; Theoretical investigation of energy levels, dynamical aspects, ...etc.
(i) Hydrogen atom line spectrum
(ii) Photoelectric effect
(iii) Frequency dependence of black body radiation
(i) Hydrogen atom line spectrum

Hydrogen line spectrum

(ii) Photoelectric effect

Photon
electromagnetic radiation as a particle
with energy, E= nhn (n = 0, 1, 2, …)

1
hn > Ф Ek = me v 2 = hn - F
2 (Ф = work function)

Collision between electromagnetic radiatio

hn < Ф
n, i.e., photons, and electrons.

→ Energy transfer
from photon to electron.
→ E(photon) = Ф + KE(electron)
(iii) Frequency dependence of black body radiation
*. Planck Quantum theory ; E=nhν

*. de Broglie wavelength ; p =h/ λ

*. Heisenberg uncertainty principle ; ΔpxΔx ≥ ℏ

ΔtΔE ≥ ℏ

*. Dirac's relativistic QM ; Electron spin

Nuclear spin
The Schrödinger equation ;
r 2 dr sin q dq df

HΨ=EΨ
• Many-body time-independent Schrödinger equation

ĤY = EY

Nuclear Electronic Nuclear- Nuclear- Electron-

kinetic (TN) kinetic (Te) nuclear (VNN) electron (VNe) electron (Vee)
energy energy repulsion attraction repulsion

Tˆ Vˆ
• Born-Oppenheimer approximation
→ The motion of electrons is much faster than that of nuclei.
(me/M = 1/1836 for hydrogen atom)
→ The nuclei can be considered fixed while electrons move.
→ The motions of electrons and nuclei can be decoupled and treated separately.

Ĥ = T̂N + VˆNN + T̂e + VˆNe + Vˆee

Ĥ N Ĥ e
* Selection rule
• Selection rule for hydrogenic atom

(n ,l ,m )
1 1 l1
emission
absorption
(n ,l ,m ) + hn
2 2 l2
photon (s = 1)

Dl = ±1 Dml = 0,±1
Example: d orbital (l = 2) s orbital (l = 0) + hn (s = 1)

• Spin selection rule → Only transitions with same multiplicity are allowed.

singlet states triplet states

no transition
* Selection rule
with normalized yv
• Expectation value of the property in a Quantum Mechanics
can be obtained by evaluating the expectation value of the W = ò yv*Ŵy dx
v
corresponding operator.

Classical background: For an atom or molecule to be able

to interact with the electromagnetic field and to absorb or
create a photon of frequency n, it must possess a dipole
oscillating at that frequency. (resonance)
• Selection rule
A statement about which transition is forbidden or allowed.
→ Conservation of intrinsic spin angular momentum of photon (s = 1)

• Gross selection rule

specifies the general features a molecule must have if it is to have a spectrum of a
given kind. (e.g., rotational spectrum : permanent electric dipole moment)

• Specific selection rule

express the allowed transition in terms of the changes in quantum numbers.
* Fermi golden rule : two-level system
Fermi golden rule: a formula that describes the transition rate (the probability of a transition per unit time)
from one energy eigenstate of a quantum system to a group of energy eigenstates in a continuum

integration factor

* N(E) : density of final state