Quantum theory and atomic

spectroscopy
Lecture 8
Many electron atoms
Quantum mechanics is brilliant!
• Solve the Schrödinger equation for
hydrogen in spherical co-ordinates with a
fixed nucleus
• Not only do we get the wavefunctions, but
we also get the energies of the orbitals
too!
• So what about the rest of the periodic
table…..
But it doesn’t really handle SPIN….
 Today’s question is……
• Can we solve the
Schrödinger
equation for
many electron
atoms, find their
wavefunctions
and energies and
explain the
periodic table?
Well, no!
 The Schrödinger equation for
helium
• This is a many particle system
• If we assume that the nucleus is stationary, we
find the Schrödinger equation is

2 2
Hˆ = − 2 ∇ el1 − 2 ∇ el 2 + V (r1 , r2 , r12 )
h 2 h 2

8π me 8π me

2q 2 2q 2 q2
V(r1 , r2 , r12 ) = − − +
4πε 0 r1 4πε 0 r2 4πε 0 r12
 Electron correlations
• Electrons are not truly
independent of one
another
• This is known as
electron correlation and
is the result of the
repulsive interaction
between the electrons
• Even this simple 2
electron problem cannot
So introduce APPROXIMATIONS
be solved analytically
 The orbital approximation
• We use the hydrogen
wavefunctions as the
basis for the many-
electron
wavefunction e.g 1s2
• The increased
nuclear charge
means more
“compact” orbitals
• But what about the
electron correlation?
Ψ (r1 , r2 ,.....rN ) = ϕ(r1 )ϕ(r2 ).....ϕ(rN )
 Effective nuclear charge
• We introduce simple
concepts to deal with
the electron-correlation
effects and explain
relative energies
• Shielding effects
• Penetration of electron
wavefunctions
 The two electron atom
• Helium is a true two-electron atom, but others
can be treated in this way e.g. calcium
• In its ground state it has a filled orbital, but in its
excited states this is usually no longer true.
• What will these wavefunctions be like?
Degenerate wavefunctions
• Look at two electrons in
just two possible orbitals:
1s and 2s (a two level
atom again!)
• Remember using quantum
mechanics we have four
different total energies,
where classically we would
expect three
• Where do we get the extra
level?
 Superposition
Two electrons in two levels leads to four
distinct configurations
Quantum – four different total energy states
(SUPERPOSITION of c2 + c3)
 These wavefunctions are
indistinguishable!
• The simplest two-electron wavefunctions to
form would be just products of the orbitals
• These two degenerate wavefunctions are for all
intents and purposes identical
• To see this, just consider ionisation of the
helium- which electron has been ionised?
• Also, they are not orthogonal
• Known as product states ψ 1s (1)ψ 2s (2)

ψ 2s (1)ψ 1s (2 )
 Superposition of wavefunctions
• The true wavefunction is thus a superposition of
the two orbital product wavefunctions

ψ 1s (1)ψ 2s (2 ) ψ 2s (1)ψ 1s (2 )

a (ψ 1s (1)ψ 2 s (2 )) + b(ψ 2 s (1)ψ 1s (2 ))

• This clearly shows that orbitals really are only an

approximation to the real two electron
wavefunction
 Looks familiar….
• This is very similar to the free particle, where we
had two possible solutions

aψ 1s (1)ψ 2s (2 ) + bψ 2s (1)ψ 1s (2 )
− ikx
ae ikx
+ be
• The adding of wavefunctions in this way is called
SUPERPOSITION
• This time, however, we have a BOUNDARY
CONDITION….
 Symmetric and anti-symmetric
wavefunctions
• Ensure superposition produces orthogonal
wavefunctions
• There are only two solutions found in this
case Do these have the same energy? Let’s look
at the wavefunctions…

Ψ+ (1,2 ) = a [ψ 1s (1)ψ 2s (2 ) + ψ 2s (1)ψ 1s (2 )]

Ψ− (1,2 ) = a [ψ 1s (1)ψ 2s (2) − ψ 2s (1)ψ 1s (2 )]

 Seeing electron correlation
• The two (radial)
wavefunctions are
very similar, except
at very short
distances from the
nucleus
• Notice there is an
(anti)-correlation
between the
electrons
 Fermi-heaps and Fermi-holes
• The anti-symmetric
wavefunction has an
decreased probability of
finding both electrons
near the nucleus. This is
a Fermi-hole.
• By contrast, the
symmetric wavefunction
has a Fermi-heap
• Both are a result of the
superposition of the 1s2s
product wavefunctions
(configurations)
Energy effect of electron correlation
• The increased magnitude of the two-electron
wavefunction at the nucleus decreases the stability of
the symmetric wavefunction because of the electron-
electron repulsion!

• Key here is that the electron repulsion does not “create”

the Fermi-hole, but it does effect the final energy of the
wavefunctions!
The helium atom again
• We seem to have two
sets of energy levels
• They correspond to
different values of
total spin
• Orthohelium energy
levels much lower!
• Now, we’ll draw this a
slightly different
way…
 Spatial wavefunctions
This time,
notice that all
singlet terms
are symmetric
spatial
wavefunctions,
and the anti-
symmetric
triplet!

• This is due to a fundamental symmetry of quantum

objects…. but we’ll leave it till next year!!!
Answers to the earlier questions..
• We cannot solve a
Schrödinger equation for
many electron atoms
analytically
• Instead, we introduce some
approximations and use
numerical techniques to help
us
• Electron correlations can be
revealed in many-electron
wavefunctions, such as
Fermi heaps and holes
• Superposition of product
wavefunctions is imposed by
the indistinguishability of
electrons
 To summarise
• Quantum mechanics was a marriage between
experimental observation and theoretical insights
• The key seems to be people willing to think the
unthinkable!