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CHEM F111 General Chemistry Lecture 09

Hydrogenic atom spectra, Electron
spin and Many electron atoms
 Review of lecture 08

• Hydrogenic orbital analysis

• General form of a radial wavefunction

• Orientation expressive orbitals vs L z eigenfunctions

• Orthogonality, orthonormality, Hermitian operators
• Hybrid orbitals
• Radial wavefunctions, probability density and radial
probability distribution for ground state
• Radial function graphs and 3D electron density
contours
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1s wavefunction and probability
density

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Radial probability distribution

Radial probability distribution function: Probability that

electron will be found between r and r+dr from the
nucleus, regardless of the angle/direction. For s
orbitals, Volume element dxdydz = r2drsinθdθdφ

P(r)dr = 4πr2R2dr (for orbitals with l=0, i.e., s-orbitals)

More generally P(r) = r2R2(r); (for orbitals with l>0)

where R(r) is the radial wavefunction

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Radial probability distribution
for 1s state
Most probable distance from the nucleus = a0

How to obtain this? Set dP(r)/dr = 0 and calculate r

P(r) = r2R2(r)

For the 1s orbital P(r) = (4/a03) 4πr2 e-2r/a0

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Radial wavefunctions
Homework:
Using the expressions
for R(r) provided in
the additional course
material, plot Rn,l(r)
versus r for 1s, 2s, 2p,
3s, 3p, 3d and obtain
the values of r
corresponding to the
radial nodes in the
orbitals.

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Electron spin

Intrinsic angular momentum, and associated magnetic

moment, characteristic of electron, a property like its
mass, charge etc.
First indicated by spectroscopic features, eg., the
doublet Na D ‘line’
Confirmed by the Stern Gerlach experiment. A beam
of atoms passed through a magnetic field strongly
inhomogeneous in, say, the z direction. Two beams
emerge – the magnetic moment can take only two
orientations with respect to the chosen axis.
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Stern Gerlach experiment

Classically
expected
result

z-axis

Experimental Result
(Ag atoms)
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Electron spin

Electron spin described by intrinsic spin angular

momentum quantum number: s = ½ Magnitude of
spin angular momentum:
[½(½+1)]½ħ = (3/4)½ħ

Orientation of spin angular

momentum is quantized
corresponding to the
quantum number ms: (In general, ms = -s,-s+1,...,s-1,s)

Consequently, for electron z-component of spin angular

moment is ħ/2 or -ħ/2, corresponding to ms = 1/2 (α) or
-1/2 (β), respectively.

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Spin angular momenta of
fundamental particles
Particles with integer spins (s=0,1,2,...) obey the
Bose-Einstein statistics and are called bosons, e.g.
photons, gluons, Higgs' bosons, etc.
According to Pauli principle, the wavefunction of a
system of bosons is symmetric with respect to the
interchange of space-spin coordinates of any two
bosons (later).
Particles with half integer spins (s=1/2,3/2,....) obey
the Fermi-Dirac statistics and hence, are called
fermions, e.g. electron, proton, neutron, etc.
According to Pauli principle, the wavefunction of a
system of fermions is anti-symmetric with respect to
the interchange of space-spin coordinates of any two
fermions (later).
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Emission spectra of hydrogenic
atoms
Selection rules: The allowed transitions are those
during which, the orbital angular momentum
quantum number of the atom changes by one
unit. The magnetic quantum number may change
at the most by one unit. The spin angular
momentum remains unchanged during the
transition.
Δl=±1, Δml=0,±1, Δms=0
Origin? Conservation of angular momentum:
Photon has spin angular momentum = 21/2ħ
corresponding to s=1

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Grotrian diagram

Δl=±1, Δml=0,±1

Δms=0

(Obviously, Δn≠0)

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Many electron atoms

Hamiltonian:
2 2 2 2 2
ℏ 2 ℏ 2 2 Ze Ze e
− ∇N− ( ∇ 1 + ∇ 2 +…)− − −…+ +…
2 mN 2 me 4 π ϵ 0 r 1 4 π ϵ0 r 2 4 π ϵ0 r 12

(K.E)N (K.E.)e VNe Vee

The Schrödinger equation cannot be solved exactly for

atoms with two or more electrons. (Vee is the bottleneck –
due fast motion of electrons)
However, refined approximations allow one to compute
wavefunctions and energies quite accurately.
Consider Vee in approximate way – make separable
Hamiltonian

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Pauli principle

When the labels of any two identical fermions (½

integer spin) are exchanged, the total wavefunction
(including spin) changes sign. (ANTISYMMETRIC under
exchange)
Fermions ψ(2,1) = -ψ(1,2)

When the labels of any two identical bosons (integer

spin) are exchanged, the total wavefunction (including
spin) remains the same. (SYMMETRIC under exchange).

Bosons ψ(2,1) = ψ(1,2)

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Many electron atoms: Orbital
approximation
Wavefunction for many-electron atom: Ψ(1,2,…)
Pauli principle says that the wavefunction should be
antisymmetric with respect to interchange of space-
spin coordinates of any two electrons.
Orbital approximation: Approximate the wavefunction
as a product of one electron functions or orbitals.
Ψ(1,2,…) = ψ1(1)ψ2(2)….. {multiplied by spin parts}*
How correspondingly are we approximating the
Hamiltonian? Each orbital may be thought of as being
hydrogen-like with an effective nuclear charge (effect
of average e-e repulsion included).
*antisymmetry to be ensured
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Spin-orbitals
Spin-orbital is one electron function multiplied by electron-
spin function.
e.g. Hydrogenic spin-orbitals: State of a hydrogenic atom is
completely described by hydrogenic spin-orbitals
(characterized by four quantum numbers: n, l, ml and ms).
1s_α → n=1, l=0, ml=0, ms=1/2
1s_β → n=1, l=0, ml=0, ms=-1/2
2pz_α → n=2, l=1, ml=0, ms=1/2
2p1_β → n=2, l=1, ml=1, ms=-1/2; and so on.
Hydrogenic spin-orbitals describe the electronic state of the
hydrogenic atom completely.
For a many electron atom, with the wavefunction described
using orbital approximation, no two electrons can have same
spin-orbital according to Pauli principle.
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Form of many electron
wavefunctions: two-electron case
Two electrons in same orbital (spatial wavefunction) Φ:

ψ(1,2) = Φ(1)Φ(2){spin part}

Pauli principle: ψ(1,2) = -ψ(2,1) (MUST FOLLOW!)
How the spin part could be?
α(1)
  α(2)
  or β(1)
 β(2)
 

(same spin) ?

α(1)
  β(2)
  or β(1)
 α(2)
 

(opposite spin) ?
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Form of two-electron
wavefunction; paired electrons
What will be the form of the wavefunction?
ψ(1,2) = Φ(1)Φ(2) α(1)β(2) ?
ψ(1,2) = Φ(1)Φ(2) β(1)α(2) ?
ψ(1,2) = 2-1/2Φ(1)Φ(2) { α(1)β(2)+β(1)α(2)} ?
ψ(1,2) = 2-1/2Φ(1)Φ(2) { α(1)β(2) - β(1)α(2)} ?

The only form that leads to antisymmetric

wavefunction with respect to exchange of the
electrons' coordinates is:
ψ(1,2) = 2-1/2Φ(1)Φ(2) { α(1)β(2) - β(1)α(2)}

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Antisymmetry in electronic
states with unpaired electrons
What will be the valid forms of the spatial part of the
wavefunction?
ψ(1,2)spatial = 2-1/2[Φ1(1)Φ2(2)+Φ2(1)Φ1(2)] (A)

ψ(1,2)spatial = 2-1/2[Φ1(1)Φ2(2) - Φ2(1)Φ1(2)] (B)

Form (A) is symmetric and when multiplied with

antisymmetric spin part will result in antisymmetric
wavefunction. Form (B) being antisymmetric, requires
the spin part to be symmetric for antisymmetric
wavefunction

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Antisymmetry in electronic
states with unpaired electrons
Antisymmetric spin part – only one valid form: (singlet)
MS=0 → 2-1/2[α(1)β(2)-β(1)α(2)]

Symmetric spin part – three possibilities: (triplet)

MS=1 → α(1)α(2); MS=-1 → β(1)β(2)

MS=0 → 2-1/2[α(1)β(2)+β(1)α(2)]
Thus, the valid wavefunctions are:
Ψs(1,2)= 0.5[Φ1(1)Φ2(2)+Φ2(1)Φ1(2)][α(1)β(2)-β(1)α(2)]

Ψ1t(1,2)= 2-1/2[Φ1(1)Φ2(2)-Φ2(1)Φ1(2)][α(1)α(2)]

Ψ2t(1,2)= 0.5[Φ1(1)Φ2(2)-Φ2(1)Φ1(2)][α(1)β(2)+β(1)α(2)]

Ψ3t(1,2)= 2-1/2[Φ1(1)Φ2(2)-Φ2(1)Φ1(2)][β(1)β(2)]
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Orbital approximation: He atom

The orbital approximation allows us to express the

electronic structure of an atom in terms of its
configuration, the list of occupied orbitals.
For example, if one disregards the inter-e;ectronic
repulsion, the ground state wavefunction of He may
be written as
ψ(1,2) = (8/πa03)1/2exp(-2r1/a0)(8/πa03)1/2exp(-2r2/a0)
corresponding to the configuration 1s2, with the 1s
orbital being somewhat more compact than in H.
What about Li? (Can all 3 electrons occupy 1s
orbital ?)

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Orbital approximation

No two electrons can have same spin-orbital. (Pauli

principle revisited)
If two electrons have same spatial orbital, then their
spins must be different (paired).
The two electrons with paired spins have zero net spin
angular momentum. (S=0, hence, MS=0).
An orbital can accommodate maximum two electrons.
This principle forms the basis of the electronic
structure of atoms, chemical periodicity, and
molecular structure.
The third electron in Li must enter the n = 2 shell, but
the 2s or the 2p?
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Shielding

In a many electron atom, each electron is shielded

from the nucleus by the others, and to a first
approximation, each electron may be thought of as
experiencing an effective nuclear charge.

The effective nuclear charge experienced by an

electron will be determined by its probability density
distribution, and this in turn by its wavefunction

Electrons in s-type orbitals shield more effectively than

the ones in p-type, d-type,... orbitals.

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Penetration

The radial probability distribution function for s-type

orbitals is greater than the p-, d-, etc type orbitals of
the given shell.

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Order of occupation
The penetration of an ‘s’ electron is greater as
compared to a ‘p’ electron of the same shell implies
that it experiences a greater effective nuclear charge.
In turn, the effective nuclear charge experienced by
the ‘p’ electron will be greater than that for a ‘d’
electron in the same shell. In general therefore, in the
same shell of a many-electron atom, the order of
energies of the subshells is s < p < d < f.

Thus, the ground electronic configuration of Li is

therefore 1s22s1, or [He]2s1.
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Order of occupation

Aufbau principle: (Building up principle)– The subshells

are occupied in the sequence:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p,
7s, …

Every orbital has two spin-parts resulting in two spin-

orbitals. Thus, every orbital can accommodate two
electrons. Consequently, a subshell with azimuthal
quantum number, l, can accommodate 4l+2 electrons.

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Ground state electronic
configuration (under orbital approximation)
H: 1s1 F: [He]2s22p5

He: 1s2 Ne: [He]2s22p6

Li: 1s22s1 → [He]2s1 Na: [He]2s22p63s1 → [Ne]3s1

Be: 1s22s2 → [He]2s2 Al: [Ne]3s23p1

B: 1s22s22p1 → [He]2s22p1 Ar: [Ne]3s23p6

C: 1s22s22p2 → [He]2s22p2 Sc: [Ar]3d14s2

N: 1s22s22p3 → [He]2s22p3 Zr: [Kr]4d15s2

O: 1s22s22p4 → [He]2s22p4 Ce: [Xe]4f15d16s2

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Electronic configuration of
atoms
Question: How many states of a Carbon atom
correspond to the electronic configuration: 1s22s22p2 ?
Answer: The 1s and 2s subshells are completely filled.
The two electrons in 2p subshell can be arranged in
6
C2 = 15 possible ways → 15 states.
Question: Are all these states energetically
degenerate?
Answer: No. Not all of them have same energy.
Question: What are the factors affecting the energies
of these states?
Answer: Coupling of the spin and orbital angular
momenta – spin orbit interactions.

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Electronic configuration of
atoms
l HIGH ENERGY
Magnetic moments are
parallel (angular
momenta are parallel)
s
l LOW ENERGY
Magnetic moments are
antiparallel (angular
momenta are
antiparallel)

Energy depends on relative orientation of spin- and

orbital- angular momenta
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Spin orbit coupling

Energy of the spin-orbit coupling depends on

E α {j(j+1) – l(l+1) – s(s+1)}
For electron, s= ½;
If orbital angular momentum is zero then; l=0 →
j=s=½
E α {j(j+1)–l(l+1)–s(s+1)} ={½(½+1)–0 –½(½+1)}=0
No spin orbit coupling.
In other cases, spin-orbital coupling will result in
change in the energy → different energy levels obtained

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