Quantum Mechanics for Chemical Engineers Lecture 14

Atomic Structure and Spectra:

Byungchan Han
Department of Chemical & Biomolecular Engineering,Yonsei University
April 26, 2016 (Tuesday)
 Building-up (= Aufbau) Principle
1. Imagine the bare nucleus of atomic number Z, and then feed into the orbitals Z electrons in succession.
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s …
2. Each orbital may accommodate up to two electrons.
6C: 1s22s22p2 or [He] 2s22p2

Degenerated px, py, pz orbital.

Can we expect the last two electrons to occupy different 2p orbitals? —> electrons will then be
further apart on average and repel each other less than if they were in the same orbital.

3. Electrons occupy different orbitals of a given subshell before doubly occupying anyone of them.
7N: [He] 2s22p 12p 12p 1
x y z
8O: [He] 2s22p 22p 12p 1
x y z

4. Hund’s Maximum Multiplicity rule: An atom in its ground state adopts a configuration with the
greatest number of unpaired (parallel) electrons.

Max-Born —> Friedrich Hund (1896- 1997, 101) —> Edward Teller —> Lee & Yang

Spin-Correlation
Electrons with parallel spins behave as if they have a tendency to stay well apart,
and hence repel each other less.
In essence, the effect of spin correlation is to allow the atom to shrink slightly, so
the electron–nucleus interaction is improved when the spins are parallel.
 Spin Correlation

!
! r2
r1 ⎧Ψ − × [α (1)α (2)]
⎪
⎪Ψ − × [ β (1)β (2)] Acceptable wavefunctions
⎪
Ψ ⎨Ψ − × ⎡ 1 {α (1)β (2) + β (1)α (2)} ⎤
⎢⎣ 2 ⎥⎦
⎪
⎪ ⎡ 1
⎪Ψ + × ⎢ {α (1)β (2) − β (1)α (2)}⎤⎥
⎩⎪ ⎣ 2 ⎦
What happen if r1 = r2 ?

⎧
⎪Ψ × [α (1)α (2)]
⎪⎪ − there is zero probability of finding the two electrons
⎨Ψ − × [ β (1)β (2)] → vanish due to Ψ −
⎪ at the same point in space when they have parallel spins
⎪Ψ − × ⎡ 1 {α (1)β (2) + β (1)α (2)} ⎤
⎪⎩ ⎢⎣ 2 ⎥⎦
Because the two electrons have different relative spatial
distributions depending on whether their spins are parallel or not,
⎡ 1 ⎤ it follows that their Coulombic interaction is different,
Ψ+ × ⎢ {α (1)β (2) − β (1)α (2)}⎥ : Not vanish and hence that the two states have different energies.
⎣ 2 ⎦
10Ne: [He]2s2 2p6 :Complete L-Shell
11Na: [Ne]3s1 — Li Period
12Mg: [Ne]3s2 — Be Period
 Transition Metals:(d-orbitals, 10 electrons)

• Energy of 3d and 4s?

• Electron–electron repulsions?
• The most probable distance from the nucleus

21Sc [Ar] 3d14s2 21Sc: [Ar]3d14s2 Not [Ar]3d3 Nor [Ar]3d24s1

22Ti [Ar] 3d24s2
23V [Ar]3dn4s2 (where n = 1 for Sc and 10 for Zn) 4s
[Ar] 3d34s2
24Cr [Ar] 3d54s1 Exceptions: 24Cr: [Ar]3d54s1, 29Cu: [Ar]3d104s1
25Mn 4s 3d
[Ar] 3d54s2
26Fe [Ar] 3d6 4s2 When d-block elements form ions,
27Co the 4s electrons are lost first.
[Ar] 3d74s2
28Ni 26Fe3+: [Ar] 3d5
[Ar] 3d84s2
29Cu [Ar] 3d104s1 Balance of repulsions and the size of the 3d
30Zn [Ar] 3d104s2 energy gap between the 3d and 4s orbitals
Cr: [Ar] 3d5 4s1 W: 5d4 6s2
 Transition Metals: Crystal Field Theory
• The existence of the d-block elements reflects the stepwise occupation of the 3d (4d, 5d) orbitals
• The subtle shades of energy differences and effects of electron–electron repulsion along this series
give rise to the rich complexity of inorganic d-metal chemistry.
• A similar intrusion of the f orbitals in Periods 6 and 7 accounts for the existence of the f block of the
• periodic table (the lanthanoids and actinoids).
Transition Metals: Crystal Field Theory
 Ionization Energy and Electron Affinity

• Zeff(Li) = 1.3
• Be > B
• N>O

Standard Enthalpy of Ionization (> 0) Electronic Affinity (Eea) E released when an electron
attaches to a gas-phase atom
M (g) → M + (g) + e− (g) M (g) ← M + (g) + e− (g)
T
Δ ion H (T ) = Δ ion H (T = 0) + ∫ ΔC po dT
o o
5
0 Δ eg H o (T ) = −Eea − RT Δ eg H o (X) = −Δ ion H o (X − )
5 2
Δ ion H (T ) = I1 + RT
o

2
 Atomic Spectra
• Atomic Spectroscopy (lines in the spectrum by emission or absorption) occur when the electron
distribution in an atom undergoes a transition with a change of energy (|∆E|) and emits or absorb
ΔE ⎞ ⎛ 1 ΔE ⎞
a photon of frequency ⎛⎜ ν = c = and wavenumber ⎜⎝ ν̂ = = ; 8065.47 cm -1
~ 1 eV ⎟⎠ .
⎝ λ h ⎟⎠ λ hc

• Frequency and wavenumber of radiation emitted when transitions take place provide information
on the Electronic Energy States of atoms.
• Electronic energies states of atoms control the Chemical Properties (bonding, structure).
• Allowed spectroscopic transitions of atoms are governed by selection rules that stem from
the unit angular momentum of a Photon and the Conservation of angular momentum.

A Grotrian diagram that summarizes the appearance

The emission spectrum of Na. Two very and analysis of the spectrum of atomic hydrogen.
close emissions at 589.0 and 589.6 nm. The thicker the line, the more intense the transition.
 Atomic Spectra
1. Not all Transitions are allowed!: Electron cannot transits from any initial orbitals to any other orbital.
2. Conservation of Angular Momentum: Photon has an intrinsic Spin angular momentum (s = 1).
3. The change in angular momentum of the electron must compensate for the angular momentum
carried away by the photon.
4. There is a Selection Rule: allowed transitions in terms of the changes in quantum numbers.

Δl = ±1, Δml = 0, ± 1

The principal quantum number n can change by any amount consistent with the Δl.

⎧ ΔS = 0
Selection Rule for atoms ⎪⎪
⎨ ΔL = 0, ±1
(by Term Symbol ) ⎪
⎪⎩ ΔJ = 0, ± 1; but J = 0 ← → J = 0
 Selection Rule
Δl = ±1, Δml = 0, ±1
Identify the orbitals to which a 4d electron may make radiative transitions.
• Since l = 2, the final orbital must have l = 1 or 3.
1. 4d —> Any np orbital ( subject to Δml = 0, ±1).
2. 4d —> Any nf orbital ( subject to Δml = 0, ±1) .
3. 4d —> any ns (×), 4d —> any nd (×)

A Grotrian diagram that summarizes the appearance Walter Robert Wilhelm Grotrian
and analysis of the spectrum of atomic hydrogen. (1890.4.21 in Aachen ~ 1954. 3. 3 in Potsdam)
The thicker the line, the more intense the transition.
 Spectra of Complex Atoms
Actual energy levels are not given solely by the energies of the orbitals, because
1. Electrons interact with one another in various ways.
2. Additional energetic contributions to the energy levels.: Spin-Orbit Coupling

⎧
⎪α (1)α (2)
⎪
Triplet (Spin Parallel) State ⎨β (1)β (2)
No net Spin ⎪ 1
Angular moment ⎪ {α (1)β (2) + β (1)α (2)}
⎩ 2
S=0 1
Singlet(Spin Paired) State: {α (1)β (2) − β (1)α (2)}
2
Two electrons with paired spins form a singlet state;
1
Singlet: {α (1) β (2) − β (1)α (2)} if their spins are parallel, they form a triplet state.
2

2He: 1S2
—> 1S12S1
α (1)α (2) 1
{α (1)β (2) + β (1)α (2)} β (1)β (2) Singlet or Triplet?
2
S=1 S=1 S=1
 Spectra of Complex Atoms
Actual energy levels are not given solely by the energies of the orbitals, because
1. Electrons interact with one another in various ways.
2. Additional energetic contributions to the energy levels.: Spin-Orbit Coupling

⎧
⎪α (1)α (2)
⎪
Triplet (Spin Parallel) State ⎨β (1)β (2)
⎪ 1
No net Spin ⎪ {α (1)β (2) + β (1)α (2)}
Angular moment ⎩ 2
1
S=0 Singlet(Spin Paired) State: {α (1)β (2) − β (1)α (2)}
2

Two electrons with paired spins form a singlet state;

1
Singlet: {α (1) β (2) − β (1)α (2)} if their spins are parallel, they form a triplet state.
2

α (1)α (2) 1
{α (1)β (2) + β (1)α (2)} β (1)β (2)
2
S=1 S=1 S=1
 Spectra of Complex Atoms
2 2 1 1 For states arising from the same configuration (1s12s1)
!!!!!!!!!!"1s 2s
He :1s excitation
Etriplet < Esinglet (spin correlation), ∆E ~ 0.8 eV

Spectrum of 2He is more complicated than that of atomic H, but there are two simplifying features.
1. The only excited configurations necessary to consider are of the form 1s1nl 1 .
• Only one electron is excited.
• Excitation of 2 electrons requires an energy greater than the ionization energy of the atom, so
the He+ ion is formed instead of the doubly excited atom.
2. No radiative transitions take place between singlet and triplet states because the relative orientation
of the two electron spins cannot change during a transition. ∆S = 0
• Two kinds of spectrums: between singlet states (Parahelium) and between triplet states
(Orthohelium) but not between the two.

Spin Correlation; Spin-Spin Interaction

1 The parallel spins make the spin part of the wavefunction symmetric.
2 The total wavefunction for the electrons must be anti-symmetric (fermions and Pauli exclusion principle).
3 Space (radial) part of the wavefunction to be anti-symmetric.
4 An anti-symmetric space wavefunction for the two electrons implies a larger average distance between them than
a symmetric function of the same type. The probability is the square of the wavefunction, and from a simple
functional point of view, the square of an antisymmetric function must go to zero at the origin.
5. In general, the probability for small separations of the two electrons is smaller than for a symmetric space
wavefunction.
6. If the electrons are on the average further apart, then there will be less shielding of the nucleus by the ground
state electron, and the excited state electron will therefore be more exposed to the nucleus. This implies that it will
be more tightly bound and of lower energy.
 Helium Energy Levels

• Ionization Energy & Shielding

• Spectroscopic Notation (Term Symbol)

for Multi-electron Atoms

• S = 0, singlet state, Parahelium

• S = 1, triplet state, Orthohelium
 Spin-Orbit Coupling
Spin–orbit coupling is a magnetic interaction between spin and orbital magnetic moments.
Magnetic field caused by the electron's orbital motion interacting with the spin magnetic moment.
This magnetic coupling is the cause of the splitting of a configuration into levels.

Spin-Orbit Splitting in Na
• Zeeman Effect: when atomic spectral lines are split
by the application of an external magnetic field
• Internal Zeeman Effect: the spin-orbit interaction is
also a magnetic interaction, but with the magnetic
field generated by the orbital motion of an electron
within the atom itself.
~ 0.3 Tesla, agreed with observation in in H fine structure
 Spin-Orbit Coupling
The strength of the coupling, and its effect on the energy levels of the atom, depend on
the relative orientations of the spin and orbital magnetic moments.
How to calculate the total angular momentum of electron? Vector sum of its spin and orbital momenta.

The total angular momentum of an electron is described by the

quantum numbers j and mj.
The j = l + ½ (when the two angular momenta parallel) or j = l − ½
(when they are anti-parallel).
The different values of j that can arise for a given value of l label the
levels of a term.

Identify the levels that may arise from the configurations

(a) d1 : l =2, —> 5/2 or 1/2
(b) s1 : l =0, —> ½ (Only One Level)

Energy levels with quantum numbers of j, l, and s

The coupling of the spin and orbital
hcA { j ( j + 1) − l ( l + 1) − s ( s + 1)}
angular momenta of a d electron (l = 2) 1 !
E j,l,s =
gives two possible values of j depending 2
on the relative orientations of the spin and
orbital angular momenta of the electron.
Energy levels with quantum numbers of j, l, and s

= hcA { j ( j + 1) − l ( l + 1) − s ( s + 1)}; A! ~ Wavenumber unit

1 !
E j,l,s
2

E of a magnetic moment µ in a magnetic field Β

! ! ! !
E = −µ ⋅ B ∞ s ⋅ l
! ! !
j = s +l
! ! ! ! ! ! ! !
( )( )
j ⋅ j = j = s + l ⋅ s + l = s + l + 2s ⋅ l
2 2 2

! ! 1 2 2 2
→ s ⋅l =
2
{
j −s −l }

Then, the expectation value is

! !
j,l, s s ⋅ l j,l, s = j,l, s j 2 − s 2 − l 2 j,l, s = { j ( j + 1) − l ( l + 1) − s ( s + 1)} ! 2
1 1
2 2
The unpaired electron in the ground state of an alkali metal atom has l = 0, so j = ½.
Because the orbital angular momentum is 0 in this state, the spin–orbit coupling energy is 0.
When the electron is excited to an orbital with l = 1, it has orbital angular momentum and can give rise to a
magnetic field that interacts with its spin. In this configuration the electron can have j =3/2 or j =½.
The energies of these levels are

The energy-level diagram for the formation

of the sodium D lines.
The coupling increases sharply with atomic number (as Z4 ). Whereas it is only small in H (giving
rise to shifts of energy levels of no more than about 0.4 cm−1), in heavy atoms like Pb it is very
large (giving shifts of the order of thousands of reciprocal centimeters).
 Fine Structure due to Spin-Orbit Coupling

The emission spectrum of Na. Two very

close emissions at 589.76 and 589.16 nm.

hcA { j ( j + 1) − l ( l + 1) − s ( s + 1)}
1 !
E j,l,s =
2 The energy-level diagram for the formation
ΔE j, j ′ 1 ! 1 ⎧3⎛ 3 ⎞ 1 ⎛ 1 ⎞ ⎫
= A { j ( j + 1) − j ′ ( j ′ + 1)} = A! ⎨ ⎜ + 1⎟ − ⎜ + 1⎟ ⎬ of the sodium D lines. In Na, the spin–orbit
hc 2 2 ⎩2 ⎝ 2 ⎠ 2 ⎝ 2 ⎠ ⎭ coupling affects the energies by about 17 cm−1 .
3!
= A = 17.2 ∴ A! = 11.5 cm −1
2

Li: 0.23 cm−1, K: 38.5 cm−1, Rb: 158 cm−1, Cs: 370 cm−1.
Note the increase of à with Z but more slowly than Z4 for these many-electron atoms.
 Spectroscopy & Term Symbols
In Multi-electron atoms a single configuration of an atom can give rise to a number of different
individual states with various energies.
Identify these states and find a way to label them with a ‘term symbol’.
The key in the term symbol is the angular momentum of the electrons that includes their orbital
angular momentum, their spin, and their total angular momentum.
Identify the allowed values of these angular momenta for atoms with more than one electron.

2S+1
{ L }J
• Letter (P, D, …): total orbital angular momentum quantum number, L.
• Left superscript: multiplicity of the term.
• Right subscript:value of the total angular momentum quantum number, J.

For several electron atoms

⎧Total orbital angular momentum quantum number, L
⎪
⎨ Magnitude of the ortibal angular momentum : L(L + 1)!
⎪ Degree of Orientations is distinguished by the quantum number M : 2L + 1
⎩ L

* The same for spin and total angular momenta

A summary of the types of interaction that are responsible

for the various kinds of splitting of energy levels in atoms.
 Total Orbital Angular Momentum
Clebsch-Gordan Series
1837 - 1912 (75)
1833 - 1872 (39)

1. The value of L (a non-negative integer) is obtained by coupling the individual orbital angular momenta
by using the Clebsch–Gordan series,

The code for converting the value of L into a letter is the same as for the
s, p, d, f, . . . designation of orbitals, but uses upper-case Roman letters

• A closed shell has zero orbital angular momentum.

• Therefore, when working out term symbols, we need consider only the electrons of the unfilled shell.
• In the case of a single electron outside a closed shell, the value of L is the same as the value of l
(for example, the configuration [Ne]3s1 has only an S term).

l1 − l2 = 0, l1 + l2 = 2 → L = 2,1,0 → D, P,S
Find the terms that can arise from the configurations. ⎧one F
(a) d2 : |l1 - l2| = 0 —> L = 4, 3, 2, 1, 0 —> G, F, D, P, S ⎧2 ⎧2 → 3,2,1 : F, D, P ⎪two D
⎪ ⎪ ⎪
(b) p3 : Coupling two electrons first. Then the third one. ⎨1 and 1 → ⎨1 → 2,1,0 : D, P,S → ⎨
⎪0 ⎪0 → 1 : P ⎪three P
⎩ ⎩ ⎪⎩one S
 Total Spin Angular Momentum: Multiplicity
2. For several electrons their total spin angular momentum quantum number, S (a non-negative integer
or half integer)

The The multiplicity of a term is the value of 2S+1

For two electrons (each of which has s = ½),

• only two total spin states are permitted (S = 0,1).
• The state of S = 0: MS = 0 (singlet)
• The state of S = 1: MS = +1, 0, −1 (triplet)
For three electrons
• Couple the third spin to each of the values of S
for the first two spins
• S = 3/2, 1/2

The multiplicity of a term is the value of 2S+1.

• When S=0, the electrons are all paired and there is no net spin (i.e., 1s2: a singlet term, 1S).
• A single electron has S = s =½: [Ne]3s1 can give rise to a doublet term, 2S.
• The configuration [Ne]3p1 is a doublet, 2P.
• When there are two unpaired electrons S = 1 —> 2S+1 = 3 —> a triplet term, such as 3D.
Singlets and triplets energies differ on account of the different effects of spin correlation.

* If there are several electrons outside a closed shell we have to consider the coupling
of all the spins and all the orbital angular momenta.
 Total Angular Momentum
Russel-Saunders (Light Atoms) or jj-Coupling (Heavier Atoms)

3. The J (non-negative integer or half integer) describes relative orientation of the spin and orbital
angular momenta of electrons.

⎧
⎪ J! = L! + S!
⎪⎪ !
Russel-Saunders (or LS ) Coupling (generally Z < 30) ⎨ L = ∑ li
⎪! i
• When spin–orbit coupling is weak ⎪S = ∑ s
• Spin-orbit coupling is effective only when all ⎪⎩ i
i

the orbital momenta are operating cooperatively.

• The permitted values of J are given by the
Clebsch–Gordan series
J = L + S , L + S − 1, . . . , |L − S|
!
jj − Coupling(heavier atoms) : J = ∑ ji = ∑ ( li + si )
i i

• When the spin–orbit coupling is large (in heavy atoms, those with high Z).
• The individual spin and orbital momenta of the electrons are coupled into individual j values, then
• these momenta are combined into a grand total, J .
Write the term symbols arising from the ground-state configurations of
(a) Na: 2S1/2 .
(b) F: 2P3/2 , 2P1/2
(c) the excited configuration 1s22s22p13p1 of C?
Atomic Energy Levels
 Hund’s Rule (by LS Coupling)
Rule 1: The term with the maximum multiplicity lies lowest in energy.
2S+1
{ L }J Spin-Spin interaction:
A symmetric spin state forces an antisymmetric spatial state
where the electrons are on average further apart and provide
less shielding for each other, yielding a lower energy
1S
0
Rule 2: For a given multiplicity, the term with the largest value of L
1D lies lowest in energy.
2

C: 1s2 2s2 2p2 3P

2

3P Orbit-Orbit interaction:
1 For large L value, some or all of the electrons
are orbiting in the same direction.: stay a larger
3P
0 distance apart on the average: less shielding:
Tight bound to nucleus

Rule 3: For atoms with less than half-filled shells, the level with the lowest value of J lies
lowest in energy.
Spin-Orbit Coupling
The scalar product S·L is negative if the spin and orbital angular momentum are in opposite directions.
Since the coefficient of S·L is positive, lower J is lower in energy.
 Selection Rule
Any state of the atom, and any spectral transition, can be specified by using term symbols.

3p1

3p1

The emission spectrum of Na. Two very 3s1

close emissions at 589.76 and 589.16 nm.

Emission spectrum of Na

Adsorption spectrum of Na
 Selection Rule

• The rule about ΔS (no change of overall spin) stems from the fact that the light does not affect the spin directly.
• The orbital angular momentum of an individual electron must change (so Δl = ±1), but whether or not this results
in an overall change of orbital momentum depends on the coupling.
• The selection rules given above apply when Russell–Saunders coupling is valid (in light atoms, those of low Z ).
If we insist on labelling the terms of heavy atoms with symbols like D, then we shall find that the selection rules
3

progressively fail as the atomic number increases because the quantum numbers S and L become ill defined as
jj -coupling becomes more appropriate.
• The singlet and triplet states (for which ΔS = ±1), while forbidden in light atoms, are allowed in heavy atoms