2024 - 물리화학2 - Ch 8

Focus 8, atomic structure and spectra
8A. Hydrogenic atoms

The importance of Atomic orbital
Bohr atomic model
Δ𝐸 = ℎ𝜐
Bohr radius : r @ n=1

The structure of hydrogenic atoms
V(r) : Coulomb potential energy

mass of electron : 9.109 x 10-31 kg
mass of proton : 1.672 x 10-27 kg (≈ mass of neutron)
The full Schrödinger equation ought to separate into two equations.

(one for the motion of the atom as a whole through space and the other for the motion
of the electron relative to the nucleus)
where μ is called the reduced mass
e0 : vacuum permittivity (유전율) = 8.854x10-12 J-1C2m-1

The structure of hydrogenic atoms
Because the potential energy is centrosymmetric (independent of angle), we can suspect that
the equation for the wavefunction is separable into radial and angular components.
radial wave equation angular wave equation
r: distance btw. nucleus and electron l : orbital angular momentum Q.N.

The radial solutions
When the electron has nonzero orbital angular

momentum, the centrifugal effect gives rise to
a positive contribution which is very large close to
the nucleus
rl
= Bohr radius = 52.9 pm

a0 = 52.9 pm
Evaluate the probability density at the nucleus of

the electron or an electron with n=2, l=1 m=0.
Evaluate the probability density at the nucleus of

the electron or an electron with n=2, l=1 m=0.
Atomic orbitals and their energies
The quantum number n is called the principal quantum number; it can take the value n=1,
2, 3, … and determines the energy of the electron.
Rydberg
constant
Ionization energy : the minimum

energy required to remove an electron
from the ground state, the state
of lowest energy, of one of its atoms in
the gas phase.
= Bohr radius = 52.9 pm

n=2,3,4,5, …
ℎ𝑐 1
𝐸= = ℎ𝜈 = ℎ𝑐 = ℎ𝑐 𝜈ҧ
𝜆 𝜆
n=2,3,4,5, …
ℎ𝑐 1
𝐸= = ℎ𝜈 = ℎ𝑐 = ℎ𝑐 𝜈ҧ
𝜆 𝜆
n=2,3,4,5, …
1 1 ℎ𝑐
𝜐ҧ = 𝑅ത𝐻 − 𝐸= = ℎ𝜈 = ℎ𝑐 𝜐ҧ
𝑛𝑖2 𝑛𝑓2 𝜆
Shells and subshells
l=n-1
# of degenerated states : 2l + 1
Expression of atomic orbitals : 1 s, 2 s, 2 px , 2 py , 2 pz , 3 s ……

s Orbitals
0≤ ∅ ≤ 2𝜋, 0 ≤ 𝜃 ≤ 𝜋
p Orbitals
0≤ ∅ ≤ 2𝜋, 0 ≤ 𝜃 ≤ 𝜋
p Orbitals
8B. Many-electron atoms

The orbital approximation
The wavefunction of a many-electron atom is a very complicated function of the
coordinates of all the electrons.
Orbital approximation :
The individual orbitals as resembling the hydrogenic orbitals, but corresponding to nuclear
charges modified by the presence of all the other electrons in the atom.
For many-electron atom, we have to consider the interaction between electron-electron and
electron-nuclear.
The helium atom (He) = two electron atom
Atomic configuration - a statement of its occupied orbitals (in its ground state)
1H atom configuration : 1 s1
2He atom configuration : 1 s2

He atom has two electrons, forming the atom by adding the electrons in succession
to the orbitals of the bare nucleus (of charge 2e).
The second electron joins the first in the 1s orbital.
How is it possible?
Rotation in three dimensions
Space quantization - Stern–Gerlach experiment
An axis defined by the direction of an externally applied electric or magnetic field.

Spin of an electron
The spin of an electron about its own axis
- identified by the experiment performed by Otto Stern and Walther Gerlach in 1921
To distinguish this spin angular momentum from orbital angular momentum (l),
we use the spin quantum number s and the spin magnetic quantum number ms, for the
projection on the z-axis.
The magnitude of the spin angular momentum is {s(s+1)}1/2ħ and the component msħ is
restricted to the 2s+1 values m s=s, s−1, …, −s.
- Fermion : Particles with half-integral spin

1 1 1
𝑠= , 𝑚𝑠 = + , −
2 2 2 - Boson : Particles with integral spin (including 0)
↑ ↓
Spin of an electron
Pauli exclusion principle
3Li atom configuration : 1 s2 2 s1 not 1 s3 !!!!
The first two occupy a 1s orbital drawn even more closely than in He around the
more highly charged nucleus (of charge 3e).
The third electron, however, does not join the first two in the 1s orbital because
that configuration is forbidden by the Pauli exclusion principle.
Electrons with paired spins, denoted ↑↓, have zero net spin
angular momentum because the spin of one electron is
cancelled by the spin of the other.
3Li atom configuration : 1 s2 2 s1 why not 1 s2 2 p1 ???

Penetration and shielding
Effective nuclear charge Zeff:
s : shielding constant
Valence electrons – introducing chemical bonds
3Li atom configuration : 1 s2 2 s1 !!!!
Because the shell with n=2 consists of two non-degenerate subshells, with the 2s orbital
lower in energy than the three 2p orbitals, the third electron occupies the 2s orbital.
This occupation results in the ground-state configuration 1 s2 2 s1, with the central nucleus
surrounded by a complete helium-like shell of two 1 s electrons, and around that a more
diffuse 2 s electron.
The electrons in the outermost shell of an atom in its ground state are called
the valence electrons because they are largely responsible for the chemical bonds that
the atom forms.
The building-up principle (Aufbau principle)
In the ground state of an atom or ion,

electrons fill atomic orbitals of the lowest
available energy levels before occupying higher
levels.
The importance of Atomic orbital
Shells and subshells
l=n-1
# of degenerated states : 2l + 1
Expression of atomic orbitals : 1 s, 2 s, 2 px , 2 py , 2 pz , 3 s ……

Hund’s (maximum multiplicity) rule
Resulting from
Spin correlation
The building-up principle + Hund’s rule
8B.7
8C. Atomic spectra

Atomic spectra of some atoms
- lines in the spectrum (in either emission or absorption)

occur when the electron distribution in an atom
undergoes a transition with a change of energy |ΔE|.
- We can expect the spectrum to give information about
the energies of electrons in atoms
Atomic spectra of some atoms
- When the electron undergoes a transition, a change of state, from an orbital with quantum
numbers n1, l1, ml1 to another (lower energy) orbital with quantum numbers n2, l2, ml2, it
undergoes a change of energy ΔE and discards the excess energy as a photon of
electromagnetic radiation with a frequency ν given by the Bohr frequency condition.
- A photon has an intrinsic spin angular momentum corresponding to s = 1 (Boson)
- Because total angular momentum is conserved, the change in angular momentum of the
electron must compensate for the angular momentum carried away by the photon.
A selection rule : allowed transition
- The principal quantum number n can change by any amount consistent with the Δl for the
transition, because it does not relate directly to the angular momentum.
Selection rule – Quantum mechanical approach
Ψ𝑓 Excited state
multiplication by − e r with components

μx=− e x , μy=− e y , and μz=− e z
Ψ𝑖 Ground state
Y1,0
Y1,±1
Selection rule – Quantum mechanical approach
from the properties of the spherical harmonics that the integral
is zero unless lf = li ± 1 and ml,f = ml,i + m.

I is not zero when
𝑧 = 𝑟 𝑐𝑜𝑠𝜃 Δ𝑙 = ±1, Δ𝑚𝑙 = 0
= 4𝜋/3 1/2 𝑟𝑌1,0
𝑥 = 𝑟 𝑠𝑖𝑛𝜃 𝑐𝑜𝑠𝜙
Δ𝑙 = ±1, Δ𝑚𝑙 = +1
= 4𝜋/3 1/2 𝑟 𝑌1,+1 − 𝑌1,−1
𝑦 = 𝑟 𝑠𝑖𝑛𝜃 𝑠𝑖𝑛𝜙
= 𝑖 4𝜋/3 1/2 𝑟 𝑌1,+1 + 𝑌1,−1 Δ𝑙 = ±1, Δ𝑚𝑙 = −1
A selection rule : allowed transition
Otherwise, forbidden transition ( I = 0)

Singlet and triplet states
only 1 way
3 possible ways
Singlet and triplet states
2He
The parallel arrangement of spins in the 1s12s1 configuration of the He

atom lies lower in energy than the anti-parallel arrangement can now
be expressed by saying that the triplet state of the 1s12s1 configuration
of He lies lower in energy than the singlet state.
The origin of the energy difference lies in the effect of spin correlation
on the Coulombic interactions between electrons, as in the case of
Hund’s maximum multiplicity rule for ground state configurations.
Because the Coulombic interaction between electrons in an atom is

strong, the difference in energies between singlet and triplet states of
the same configuration can be large.
The two states of 1s12s1 He : 0.80 eV

Spin–orbit coupling
For l = 0, (s orbital)
the only permitted value is j = 1/2
The energies of the levels with quantum numbers s, l, and j
: Spin-orbit coupling constant , unit-wavenumber (cm-1)

Term symbol
2S+1 L J
The total orbital angular momentum
The total spin angular momentum

The total angular momentum quantum number (J)
jj-coupling
Selection rule – general form
The rule about Δ S (no change of overall spin) stems from the fact
that the light does not affect the spin directly.
The rules about Δ L and Δ l express the fact

that the orbital angular momentum of an individual electron must change (so Δ l = ± 1),
but whether or not this results in an overall change of orbital momentum

depends on the coupling.
Hund’s rule

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Focus 8, atomic structure and spectra

8A. Hydrogenic atoms

Bohr radius : r @ n=1

V(r) : Coulomb potential energy

The full Schrödinger equation ought to separate into two equations.

where μ is called the reduced mass

e0 : vacuum permittivity (유전율) = 8.854x10-12 J-1C2m-1

radial wave equation angular wave equation

r: distance btw. nucleus and electron l : orbital angular momentum Q.N.

When the electron has nonzero orbital angular

= Bohr radius = 52.9 pm

Evaluate the probability density at the nucleus of

Evaluate the probability density at the nucleus of

Ionization energy : the minimum

= Bohr radius = 52.9 pm

Expression of atomic orbitals : 1 s, 2 s, 2 px , 2 py , 2 pz , 3 s ……

8B. Many-electron atoms

2He atom configuration : 1 s2

An axis defined by the direction of an externally applied electric or magnetic field.

- Fermion : Particles with half-integral spin

3Li atom configuration : 1 s2 2 s1 why not 1 s2 2 p1 ???

Effective nuclear charge Zeff:

In the ground state of an atom or ion,

Expression of atomic orbitals : 1 s, 2 s, 2 px , 2 py , 2 pz , 3 s ……

8C. Atomic spectra

- lines in the spectrum (in either emission or absorption)

A selection rule : allowed transition

multiplication by − e r with components

is zero unless lf = li ± 1 and ml,f = ml,i + m.

A selection rule : allowed transition

Otherwise, forbidden transition ( I = 0)

The parallel arrangement of spins in the 1s12s1 configuration of the He

Because the Coulombic interaction between electrons in an atom is

The two states of 1s12s1 He : 0.80 eV

The energies of the levels with quantum numbers s, l, and j

: Spin-orbit coupling constant , unit-wavenumber (cm-1)

The total spin angular momentum

The rules about Δ L and Δ l express the fact

but whether or not this results in an overall change of orbital momentum

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