Quantum Mechanics for Chemical Engineers Lecture 12

Atomic Structure and Spectra:

Hydrogenic Atom

Byungchan Han
Department of Chemical & Biomolecular Engineering,Yonsei University
April 15, 2016 (Friday)
Specification of Orbitals in a Hydrogenic Atoms

Principal Quantum Number n (1, 2, 3, …): determines the energy of the electron.
⎧ me e 4
Z 2 µe4 hcRH ⎪ R∞ ! 8ε 2 h 3c ; Rydberg Constant
En = − = − ; (n=1,2,3,...) ⎪ 0
32π ε 0 ! n
2 2 2 2
n 2 ⎨
⎪ R = µH R
⎪⎩ H me ∞

Quantum numbers l, ml come from the angular solutions, and specify the angular momentum
of the electron around the nucleus
• Angular Momentum: l(l + 1)! ;l = 0,1,...,n − 1
An electron in an orbital with quantum number ml has a z-component of angular momentum
ml ! ; ml = 0, ±1, ±2,..., ±l

n controls the maximum value of l. l controls the range of values of ml.

Specification of Orbitals in a Hydrogenic Atoms

Principal Quantum Number n (1, 2, 3, …): determines the energy of the electron.
⎧ me e 4
Z 2 µe4 hcRH ⎪ R∞ ! 8ε 2 h 3c ; Rydberg Constant
En = − = − ; (n=1,2,3,...) ⎪ 0
32π ε 0 ! n
2 2 2 2
n 2 ⎨
⎪ R = µH R
⎪⎩ H me ∞

Quantum numbers l, ml come from the angular solutions, and specify the angular momentum
of the electron around the nucleus
• Angular Momentum: l(l + 1)! ;l = 0,1,...,n − 1
An electron in an orbital with quantum number ml has a z-component of angular momentum
ml ! ; ml = 0, ±1, ±2,..., ±l

n controls the maximum value of l. l controls the range of values of ml.

⎧Orbital :l, ml
Total Wavefunction = (Orbital ) × ( Spin State ) ⎨
⎩ Spin : s ( = 1
2 ) , m s ( = ± 2 ) for an electron
1

To specify the state ( ≠ energy level) of an electron in a hydrogenic atom

we need Four quantum numbers : n,l, ml , ms
Many-electron Atoms
 Many-electron Atoms
All electrons interact.
Degeneracy of orbitals with the same value of n but different values of l is broken due
to the combined effects of Penetration and Shielding.
Independent Electron Approximation —>> Orbital Approximation (Each electron is
regarded as occupying its own orbital).
Electrons occupy the lowest energy available orbital (ground state) subject to the
requirements of the Pauli Exclusion Principle.
Hund’s Maxim Multiplicity Rule due to Electron Correlation.
 Many-electron Atoms
All electrons interact.
Degeneracy of orbitals with the same value of n but different values of l is broken due
to the combined effects of Penetration and Shielding.
Independent Electron Approximation —>> Orbital Approximation (Each electron is
regarded as occupying its own orbital).
Electrons occupy the lowest energy available orbital (ground state) subject to the
requirements of the Pauli Exclusion Principle.
Hund’s Maxim Multiplicity Rule due to Electron Correlation.

Wavefunction of a Many-electron atom is a very complicated function of the coordinates of All electrons
! ! !
Ψ(r1 , r2 ,..., rN )
Orbital Approximation
! ! ! ! ! !
Ψ(r1 , r2 ,..., rN ) ≈ ψ (r1 )ψ (r2 )ψ (r3 )...
 Many-electron Atoms
All electrons interact.
Degeneracy of orbitals with the same value of n but different values of l is broken due
to the combined effects of Penetration and Shielding.
Independent Electron Approximation —>> Orbital Approximation (Each electron is
regarded as occupying its own orbital).
Electrons occupy the lowest energy available orbital (ground state) subject to the
requirements of the Pauli Exclusion Principle.
Hund’s Maxim Multiplicity Rule due to Electron Correlation.

Wavefunction of a Many-electron atom is a very complicated function of the coordinates of All electrons
! ! !
Ψ(r1 , r2 ,..., rN )
Orbital Approximation !2 2 e2 !2 2 e2 e2
! ! ! ! ! ! Ĥ = − ∇1 − − ∇2 − +
Ψ(r1 , r2 ,..., rN ) ≈ ψ (r1 )ψ (r2 )ψ (r3 )... 2me 4πε o r1 2me 4πε o r2 4πε o r12

⎛ !2 2 e2 ⎞ ⎛ ! 2 2 e2 ⎞
Ĥ = ⎜ − ∇1 − ⎟ +⎜− ∇2 −
For a two-electron atom ⎝ 2me 4πε o r1 ⎠ ⎝ 2me 4πε o r2 ⎟⎠
⎧ Ĥ = Ĥ + Ĥ H1 H2
⎪⎪ ! ! 1
!
2
!
Orbital Approximation ⎨Ψ ( r1 , r2 ) = ψ ( r1 )ψ ( r2 )
⎪
⎪⎩ Ĥ Ψ ( ! !
r ,
1 2r ) = Ĥ 1 +(Ĥ 2 ψ )
( !
r1 )ψ ( !
r2 ) = ( E1 + E 2 )ψ ( !
r1 )ψ ( !
r2 ) = Eψ ( !
r1 )ψ ( !
r2)
 Many-electron Atoms
All electrons interact.
Degeneracy of orbitals with the same value of n but different values of l is broken due
to the combined effects of Penetration and Shielding.
Independent Electron Approximation —>> Orbital Approximation (Each electron is
regarded as occupying its own orbital).
Electrons occupy the lowest energy available orbital (ground state) subject to the
requirements of the Pauli Exclusion Principle.
Hund’s Maxim Multiplicity Rule due to Electron Correlation.

Wavefunction of a Many-electron atom is a very complicated function of the coordinates of All electrons
! ! !
Ψ(r1 , r2 ,..., rN )
Orbital Approximation !2 2 e2 !2 2 e2 e2
! ! ! ! ! ! Ĥ = − ∇1 − − ∇2 − +
Ψ(r1 , r2 ,..., rN ) ≈ ψ (r1 )ψ (r2 )ψ (r3 )... 2me 4πε o r1 2me 4πε o r2 4πε o r12

⎛ !2 2 e2 ⎞ ⎛ ! 2 2 e2 ⎞
Ĥ = ⎜ − ∇1 − ⎟ +⎜− ∇2 −
For a two-electron atom ⎝ 2me 4πε o r1 ⎠ ⎝ 2me 4πε o r2 ⎟⎠
⎧ Ĥ = Ĥ + Ĥ H1 H2
⎪⎪ ! ! 1
!
2
!
Orbital Approximation ⎨Ψ ( r1 , r2 ) = ψ ( r1 )ψ ( r2 )
⎪
⎪⎩ Ĥ Ψ ( ! !
r ,
1 2r ) = Ĥ 1 +(Ĥ 2 ψ )
( !
r1 )ψ ( !
r2 ) = ( E1 + E 2 )ψ ( !
r1 )ψ ( !
r2 ) = Eψ ( !
r1 )ψ ( !
r2)
 Many-electron Atoms
All electrons interact.
Degeneracy of orbitals with the same value of n but different values of l is broken due
to the combined effects of Penetration and Shielding.
Independent Electron Approximation —>> Orbital Approximation (Each electron is
regarded as occupying its own orbital).
Electrons occupy the lowest energy available orbital (ground state) subject to the
requirements of the Pauli Exclusion Principle.
Hund’s Maxim Multiplicity Rule due to Electron Correlation.

Wavefunction of a Many-electron atom is a very complicated function of the coordinates of All electrons
! ! !
Ψ(r1 , r2 ,..., rN )
Orbital Approximation !2 2 e2 !2 2 e2 e2
! ! ! ! ! ! Ĥ = − ∇1 − − ∇2 − +
Ψ(r1 , r2 ,..., rN ) ≈ ψ (r1 )ψ (r2 )ψ (r3 )... 2me 4πε o r1 2me 4πε o r2 4πε o r12

⎛ !2 2 e2 ⎞ ⎛ ! 2 2 e2 ⎞
Ĥ = ⎜ − ∇1 − ⎟ +⎜− ∇2 −
For a two-electron atom ⎝ 2me 4πε o r1 ⎠ ⎝ 2me 4πε o r2 ⎟⎠
⎧ Ĥ = Ĥ + Ĥ H1 H2
⎪⎪ ! ! 1
!
2
!
Orbital Approximation ⎨Ψ ( r1 , r2 ) = ψ ( r1 )ψ ( r2 )
⎪
⎪⎩ Ĥ Ψ ( ! !
r ,
1 2r ) = Ĥ 1 +(Ĥ 2 ψ )
( !
r1 )ψ ( !
r2 ) = ( E1 + E 2 )ψ ( !
r1 )ψ ( !
r2 ) = Eψ ( !
r1 )ψ ( !
r2)

Individual orbitals as resembling the hydrogenic orbitals, but corresponding to nuclear charges
(Z) modified by the presence of all the other electrons in the atom.
Orbital Approximation
 Orbital Approximation
Consequence of the Orbital Approximation
1. An Electronic Structure is expressed by the Electronic Configuration: a statement of the occupied Orbitals.
Example: He: 1s2
3. The Pauli exclusion principle limits to two the number of electrons that can occupy a given orbital.
4. The building-up principle is an algorithm for predicting the ground-state electron configuration of an atom.
5. Ionization energies and electron affinities vary periodically through the periodic table.
 Orbital Approximation
Consequence of the Orbital Approximation
1. An Electronic Structure is expressed by the Electronic Configuration: a statement of the occupied Orbitals.
Example: He: 1s2
3. The Pauli exclusion principle limits to two the number of electrons that can occupy a given orbital.
4. The building-up principle is an algorithm for predicting the ground-state electron configuration of an atom.
5. Ionization energies and electron affinities vary periodically through the periodic table.

Pauli Exclusion Principle Li: 1s3 ?

• No more than two electrons may occupy any given orbital
• If two do occupy one orbital, then their spins must be Paired (↑↓) or (α(1)β(2))
—> zero net spin angular momentum
 Orbital Approximation
Consequence of the Orbital Approximation
1. An Electronic Structure is expressed by the Electronic Configuration: a statement of the occupied Orbitals.
Example: He: 1s2
3. The Pauli exclusion principle limits to two the number of electrons that can occupy a given orbital.
4. The building-up principle is an algorithm for predicting the ground-state electron configuration of an atom.
5. Ionization energies and electron affinities vary periodically through the periodic table.

Pauli Exclusion Principle Li: 1s3 ?

• No more than two electrons may occupy any given orbital
• If two do occupy one orbital, then their spins must be Paired (↑↓) or (α(1)β(2))
—> zero net spin angular momentum

Spin Paired Electron Configuration

 Orbital Approximation
Consequence of the Orbital Approximation
1. An Electronic Structure is expressed by the Electronic Configuration: a statement of the occupied Orbitals.
Example: He: 1s2
3. The Pauli exclusion principle limits to two the number of electrons that can occupy a given orbital.
4. The building-up principle is an algorithm for predicting the ground-state electron configuration of an atom.
5. Ionization energies and electron affinities vary periodically through the periodic table.

Pauli Exclusion Principle Li: 1s3 ?

• No more than two electrons may occupy any given orbital
• If two do occupy one orbital, then their spins must be Paired (↑↓) or (α(1)β(2))
—> zero net spin angular momentum

Nobel Prize in Physics (1945)

(1900 — 1958)

Spin Paired Electron Configuration

 Orbital Approximation
Consequence of the Orbital Approximation
1. An Electronic Structure is expressed by the Electronic Configuration: a statement of the occupied Orbitals.
Example: He: 1s2
3. The Pauli exclusion principle limits to two the number of electrons that can occupy a given orbital.
4. The building-up principle is an algorithm for predicting the ground-state electron configuration of an atom.
5. Ionization energies and electron affinities vary periodically through the periodic table.

Pauli Exclusion Principle Li: 1s3 ?

• No more than two electrons may occupy any given orbital
• If two do occupy one orbital, then their spins must be Paired (↑↓) or (α(1)β(2))
—> zero net spin angular momentum

Nobel Prize in Physics (1945)

(1900 — 1958)
Pauli Principle
• When the labels of any two identical fermions are exchanged,
the total wavefunction changes sign (Anti-symmetric).
• When the labels of any two identical bosons are exchanged,
the sign of the total wavefunction remains the same.
Total Wavefunction = (Orbital) × (Spin)

Spin Paired Electron Configuration

 Pauli Principle
1. When the labels of any two identical Fermions are exchanged, the total wavefunction changes sign
: Anti-symmetric Wavefunction
2. When the labels of any two identical bosons are exchanged, the total wavefunction remains the same.
 Pauli Principle
1. When the labels of any two identical Fermions are exchanged, the total wavefunction changes sign
: Anti-symmetric Wavefunction
2. When the labels of any two identical bosons are exchanged, the total wavefunction remains the same.

Total Wavefunction = (Orbital) × (Spin) Ψ = ψ × σ (= α , β )

! ! ! !
Ψ(r1 = 1, r2 = 2) = Ψ(1,2) = −Ψ(r1 = 2, r2 = 1) = −Ψ(2,1)
!
! r2
r1
 Pauli Principle
1. When the labels of any two identical Fermions are exchanged, the total wavefunction changes sign
: Anti-symmetric Wavefunction
2. When the labels of any two identical bosons are exchanged, the total wavefunction remains the same.

Total Wavefunction = (Orbital) × (Spin) Ψ = ψ × σ (= α , β )

! ! ! !
Ψ(r1 = 1, r2 = 2) = Ψ(1,2) = −Ψ(r1 = 2, r2 = 1) = −Ψ(2,1)
!
! r2
r1
⎧ψ (1)ψ (2)α (1)α (2)
⎪ψ (1)ψ (2)β (1)β (2)
⎪
⎪ 1
Ψ ⎨ψ (1)ψ (2) {α (1)β (2) + β (1)α (2)} = ψ (1)ψ (2)σ + (1,2)
⎪ 2 Why Superposition?
⎪ 1
⎪ψ (1)ψ (2) {α (1)β (2) − β (1)α (2)} = ψ (1)ψ (2)σ − (1,2)
⎩ 2
 Pauli Principle
1. When the labels of any two identical Fermions are exchanged, the total wavefunction changes sign
: Anti-symmetric Wavefunction
2. When the labels of any two identical bosons are exchanged, the total wavefunction remains the same.

Total Wavefunction = (Orbital) × (Spin) Ψ = ψ × σ (= α , β )

! ! ! !
Ψ(r1 = 1, r2 = 2) = Ψ(1,2) = −Ψ(r1 = 2, r2 = 1) = −Ψ(2,1)
!
! r2
r1
⎧ψ (1)ψ (2)α (1)α (2)
⎪ψ (1)ψ (2)β (1)β (2)
⎪
⎪ 1
Ψ ⎨ψ (1)ψ (2) {α (1)β (2) + β (1)α (2)} = ψ (1)ψ (2)σ + (1,2)
⎪ 2 Why Superposition?
⎪ 1
⎪ψ (1)ψ (2) {α (1)β (2) − β (1)α (2)} = ψ (1)ψ (2)σ − (1,2)
⎩ 2

ψ (1)ψ (2) = ψ (2)ψ (1); Symmetric

σ + (1,2) = σ + (2,1)
σ − (1,2) = −σ − (2,1)
 Pauli Principle
1. When the labels of any two identical Fermions are exchanged, the total wavefunction changes sign
: Anti-symmetric Wavefunction
2. When the labels of any two identical bosons are exchanged, the total wavefunction remains the same.

Total Wavefunction = (Orbital) × (Spin) Ψ = ψ × σ (= α , β )

! ! ! !
Ψ(r1 = 1, r2 = 2) = Ψ(1,2) = −Ψ(r1 = 2, r2 = 1) = −Ψ(2,1)
!
! r2
r1
⎧ψ (1)ψ (2)α (1)α (2)
⎪ψ (1)ψ (2)β (1)β (2)
⎪
⎪ 1
Ψ ⎨ψ (1)ψ (2) {α (1)β (2) + β (1)α (2)} = ψ (1)ψ (2)σ + (1,2)
⎪ 2 Why Superposition?
⎪ 1
⎪ψ (1)ψ (2) {α (1)β (2) − β (1)α (2)} = ψ (1)ψ (2)σ − (1,2)
⎩ 2

ψ (1)ψ (2) = ψ (2)ψ (1); Symmetric

σ + (1,2) = σ + (2,1)
σ − (1,2) = −σ − (2,1)

Only one of the four possible states is allowed by Pauli exclusion principle
 1
Singlet (Spin Paired) State: {α (1)β (2) − β (1)α (2)}
2

⎧
⎪α (1)α (2)
⎪
Triplet (Spin Parallel) State ⎨β (1)β (2)
⎪ 1
⎪ {α (1)β (2) + β (1)α (2)}
⎩ 2
1
Singlet: {α (1)β (2) − β (1)α (2)}
2

1
α (1)α (2) {α (1)β (2) + β (1)α (2)} β (1)β (2)
2
Pauli Principle
 Pauli Principle
Total Wavefunction = (Orbital) × (Spin): Antisymmetric
 Pauli Principle
Total Wavefunction = (Orbital) × (Spin): Antisymmetric

1
Ψ = ψ (1)ψ (2) {α (1)β (2) − β (1)α (2)} = ψ (1)ψ (2)σ − (1,2)
2
 Pauli Principle
Total Wavefunction = (Orbital) × (Spin): Antisymmetric

1
Ψ = ψ (1)ψ (2) {α (1)β (2) − β (1)α (2)} = ψ (1)ψ (2)σ − (1,2)
2

1 ψ (1)α (1) ψ (2)α (2)

Ψ=
2 ψ (1)β (1) ψ (2)β (2)
 Pauli Principle
Total Wavefunction = (Orbital) × (Spin): Antisymmetric

1
Ψ = ψ (1)ψ (2) {α (1)β (2) − β (1)α (2)} = ψ (1)ψ (2)σ − (1,2)
2

1 ψ (1)α (1) ψ (2)α (2)

Ψ=
2 ψ (1)β (1) ψ (2)β (2)

Slater Determinant
• in general for N electrons in orbitals of ψa,ψb, … John Clarke Slater
(December 22, 1900 – July 25, 1976)
 Pauli Principle
Total Wavefunction = (Orbital) × (Spin): Antisymmetric

1
Ψ = ψ (1)ψ (2) {α (1)β (2) − β (1)α (2)} = ψ (1)ψ (2)σ − (1,2)
2

1 ψ (1)α (1) ψ (2)α (2)

Ψ=
2 ψ (1)β (1) ψ (2)β (2)

Slater Determinant
• in general for N electrons in orbitals of ψa,ψb, … John Clarke Slater
(December 22, 1900 – July 25, 1976)
Penetration & Shielding

Effective Nuclear Charge: Zeff= Z - σ

σ: Shielding Constant
Penetration & Shielding
Penetration & Shielding

• The average radii of the 2s and 2p orbitals are

99 pm and 84 pm, respectively.
• The extent of penetration is more important than
the average radii.
 Penetration & Shielding

• The average radii of the 2s and 2p orbitals are

99 pm and 84 pm, respectively.
• The extent of penetration is more important than
the average radii.

• An s electron has a greater penetration through inner shells than a p electron: it is more likely to be
found close to the nucleus than a p electron of the same shell.
• Because only electrons inside the sphere defined by the location of the electron contribute to shielding,
an s electron experiences less shielding than a p electron.
• Consequently, by the combined effects of penetration and shielding, an s electron is more tightly bound
than a p electron of the same shell.
• Similarly, a d electron penetrates less than a p electron of the same shell (recall that the wavefunction
of a d orbital varies as r2 close to the nucleus, whereas a p orbital varies as r1), and feels more shielding.
 Penetration & Shielding

• The energies of subshells of a shell in a many-electron atom (with the same n but different l) in general
lie in the order s < p < d < f. : Degeneracy is broken
• The individual orbitals of a given subshell (with the same l but different ml) remain degenerate because
they all have the same radial characteristics and so experience the same effective nuclear charge.
• Valence Electrons & Core Electrons
Building-up Principle (= Aufbau in German)
 Building-up Principle (= Aufbau in German)
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
 Building-up Principle (= Aufbau in German)
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.
 Building-up Principle (= Aufbau in German)
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.
 Building-up Principle (= Aufbau in German)
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
 Building-up Principle (= Aufbau in German)
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 ⎦
 4s
10Ne: [He]2s2 2p6
11Na: [He]2s2 2p63s1 — Li Period 4s 3d
12Mg: [He]2s2 2p63s2 — Be Period

Transition metals (d-orbitals, 10 electrons): Sc ~ Zn

21Sc: [Ar]3d14s2 or [Ar]3d3 or [Ar]3d24s1

[Ar]3dn4s2 (where n = 1 for scandium and n = 10 for zinc) 3d

Exceptions: 24Cr: [Ar]3d54s1, 29Cu: [Ar]3d104s1
 Transition Metals
• 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).
 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
a photon of frequency (ν = |∆E|/h) and wavenumber (=1/λ = |∆E|/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

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.
 Selection Rule: Dipole Moment

1s —> 2s 1s —> 2p
 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.
• 4d —> Any np orbital (subject to Δml = 0, ±1).
• 4d —> Any nf orbital (subject to Δml = 0, ±1).
4s —> ?
• 4d —> any ns (×), 4d —> any nd (×)

Walter Robert Wilhelm Grotrian

(1890.4.21 in Aachen ~ 1954. 3. 3 in Potsdam)
Grotrian Diagram of atomic Hydrogen.
• shows the allowed electronic transitions between
the energy levels of atoms.
• 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. the electrons interact with one another in various ways.
2. there are additional energetic contributions to the energy levels.

⎧
⎪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
For states arising from the same configuration, the triplet state generally lies lower than the singlet state
(spin correlation on the Coulombic interactions between electrons)
∆E ~ 0.8 eV for 2He (substantial)

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 1s1nl1.
• Only one electron is excited.
• Excitation of two 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.
• Thus, there is a spectrum arising from transitions between singlet states (including the ground state)
and between triplet states but not between the two.(‘parahelium’ and ‘orthohelium’)
• . The Grotrian diagram for helium in Fig. 9.26 shows the two sets of transitions.
Spin-Orbit Coupling