Scribd
Upload
77 views21 pages

2006-7 Quantum Theory Slides Lecture 8

The document discusses solving the Schrodinger equation for multi-electron atoms. It introduces approximations like the orbital approximation to deal with electron correlation effects. For the two electron helium atom, the wavefunction must be a superposition of product wavefunctions to properly account for electron indistinguishability and correlation. This leads to symmetric and anti-symmetric spatial wavefunctions corresponding to singlet and triplet energy levels. Overall, the document examines how approximations and accounting for electron correlation are needed to understand multi-electron atoms using quantum mechanics.

Uploaded by

api-19928045
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
77 views21 pages

2006-7 Quantum Theory Slides Lecture 8

The document discusses solving the Schrodinger equation for multi-electron atoms. It introduces approximations like the orbital approximation to deal with electron correlation effects. For the two electron helium atom, the wavefunction must be a superposition of product wavefunctions to properly account for electron indistinguishability and correlation. This leads to symmetric and anti-symmetric spatial wavefunctions corresponding to singlet and triplet energy levels. Overall, the document examines how approximations and accounting for electron correlation are needed to understand multi-electron atoms using quantum mechanics.

Uploaded by

api-19928045
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 21

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!

You might also like

pFad - Phonifier reborn

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


Alternative Proxies:

Alternative Proxy

pFad Proxy

pFad v3 Proxy

pFad v4 Proxy