Module 113- Quantum theory and atomic spectroscopy

LECTURE 8 - The two electron atom

19. Many electron atoms

Hydrogen is all very well, but it is hardly the Periodic Table. Why not use the Schrödinger equation to
solve the next atom along, helium, which obviously is a two electron system? Well, it’s easy enough to
write down the Schrödinger equation for this atom, but we find we cannot solve it exactly. The problem
is the Coulombic interaction between the electrons:

q2
V12 = where r12 is the inter-electron separation (8.1)
4πε 0 r12

If this interaction was removed, the Schrödinger equation for helium would boil down to two separate
hydrogenic (hydrogen like) equations, and the wavefunction simply the product of two hydrogenic
wavefunctions. Why hydrogenic? Simply because the nuclear charge has now changed to Zq, where Z is
the atomic number. Therefore, the Coulomb potential between the nucleus and the electron becomes

Zq 2
V = − (8.2)
4πε 0 r

But the electron interactions change all that. They lead to electron-electron correlation effects. The
problem in solving such many-particle equations is not unique to quantum mechanics, though the
development of approximation methods to “estimate” the true solution has been intensified by the
needs of the quantum chemists.
The most important approximation we use is to assume each electron has a particular value of the
quantum numbers n, l and ml. These sublevels or orbitals are based very much on the hydrogen
orbitals found in the last section. The orbital approximation states that the total wavefunction
Ψ (r1 , r2 ,.....rN ) is, to a first approximation, given by

Ψ (r1 , r2 ,.....rN ) = ϕ (r1 )ϕ (r2 ).....ϕ (rN ) (8.3)

where ϕ (ri ) is just the wavefunction of the electron orbital corresponding to electron i (for example, it
could be a 1s orbital). In general, the hydrogenic orbitals will be more compact than the corresponding
ones in hydrogen because of the greater nuclear charge. They will still be described by a product of
radial wavefunctions and the spherical harmonics (angular functions), as were the orbitals in hydrogen.

However, the orbital approximation does not completely ignore the electron interactions. We attempt to
include the effect of electron-electron interaction by invoking the idea of electron shielding. The
repulsive interaction between an electron and its housemates (atom mates?) reduces somewhat the
attraction of the electron to the nucleus. In effect, the nuclear charge is reduced.

Effective nuclear charge = Actual nuclear charge – electron repulsion (8.4)

The effective nuclear charge is sometimes written as Zeff. We can learn a great deal about the behaviour
of many-electron atoms by looking at the simplest one: helium, which has just two electrons.

20. The energy levels of helium

In lecture two we considered an ideal two level atom with two electrons. We can now appreciate that the
energy levels in that model approximate to the electron orbitals. Naturally, in a real atom like helium we
are not restricted to just two levels: just like for hydrogen, there are an infinite number of levels. We also
understand that orbitals sharing the same value of n but different l are not degenerate, but have different
energies. But this is not the only example of the breaking of degeneracy in a multi-electron atom.

Let’s stay with a two level helium atom, but now give the levels some real quantum numbers: n = 1 and l
= 0 for the lowest level, and n = 2, l = 0 for the upper level. If both electrons occupy the lower level, then
we have the configuration 1s2 and if they occupy the upper level, then we have 2s2. The resulting
wavefunction for 1s2 would therefore be written as ψ 1s (1)ψ 1s (2 ) . An interesting situation arises when we
have one electron in the lower level and one in the upper level: we have two different configurations but
classically the energy would be the same. However, quantum mechanics does not produce the same
result. To see why, we must appreciate that the two configurations correspond, in the orbital
approximation, to two different wavefunctions

ψ 1s (1)ψ 2s (2) ψ 2s (1)ψ 1s (2 ) (8.5)

Electrons are identical particles: every electron has the same mass, charge and spin. If we ionise the
helium and the electron is ejected from the 2s orbital, we cannot know which electron it was. In addition,
these two product wavefunctions are not orthogonal, so are not acceptable solutions. When we have
more than one possible solution, quantum mechanics tells us that the true wavefunction is in fact a
superposition of the possible wavefunctions (8.5).

aψ 1s (1)ψ 2s (2 ) + bψ 2s (1)ψ 1s (2 ) (8.6)

Now this looks very much like the situation we had with the free-particle which would be bad news
because that allowed an infinite number of potential wavefunctions. But we know that this could not be
the case because helium has a line spectra, just like all the other elements and thus quantised energy
levels. What we have in helium and not for a free-particle is the presence of a
boundary condition that restricts the acceptable wavefunctions: the resulting spatial
wavefunctions must be orthogonal to one another in order that they are truly separate eigenfunctions of
the Hamiltonian. Now we find that the coefficients a and b can only take two sets of values and so there
are only two possible ways we can add the wavefunctions together:

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

(8.7)
Ψ− (1,2 ) = a [ψ 1s (1)ψ 2s (2 ) − ψ 2s (1)ψ 1s (2 )]

The top wavefunction is a symmetric wavefunction, while the bottom one is the antisymmetric
wavefunction. If we multiple the two wavefunctions together and integrate over all space the result is
zero, which proves that the two new wavefunctions are orthogonal. Another way to think of this is that at
the very beginning we stated that the individual orbitals were an approximation of the true helium
wavefunction. The symmetric and anti-symmetric wavefunctions are just much closer to the truth as we
will now see.

A consequence of forming the two new wavefunctions is that because the two wavefunctions are different
we find that by inserting each one into the Schrödinger equation that they have different energies. Thus
the two states are no longer degenerate. One prominent difference is that in the symmetric
wavefunction there is a significant probability of finding the two electrons in the same place, notably near
the nucleus, while in the antisymmetric case the probability of finding the two electrons in the same place
is exactly zero. This is the so called the Fermi-hole.
The result of this hole is that in the antisymmetric case the electrons tend to avoid one another and as a
result the repulsion energy is lowered. Therefore the antisymmetric wavefunction has a lower energy than
the symmetric wavefunction. This is the reason that arranging two electrons in two energy levels leads to
four different total energies and not three as we would expect classically. You may find all this hard to
believe just yet but this situation is very similar to what happens when you bring two atoms together to
make a chemical bond!

Finally, I cannot stress the following point enough: the Fermi hole is not the result of
electron repulsion! It is a property of the quantum mechanics, not the electronic charge. The charge
on the electron and the subsequent repulsion just ensures that the wavefunction with the Fermi-hole has
the lower energy because repulsive interactions are minimised.

To complete our study of helium we need to look again at the energy levels of the triplet and singlet
terms. Included on the diagram are examples of allowed and forbidden transitions assuming the usual
selection rules. Now we notice is that all the triplet terms have anti-symmetric spatial wavefunctions and
that all the singlet terms have symmetric spatial wavefunctions. There is an explanation for this based
on a fundamental symmetry of the Universe….but I’ll tell you all about that next year!!!
21. The postulates of quantum mechanics
Over the last two weeks you have encountered two fundamentally important concepts in the theory we
now call quantum mechanics.

1. Objects can possess a mass and a wavelength, and therefore display behaviour once associated
to either particles or waves.
2. Angular momentum plays a crucial role in our description of atoms (and molecules as it turns
out).

Soon after the work of Schrödinger and Heisenberg, some basic rules were drawn about how to proceed
when tackling the question “What does quantum mechanics tell me about the physical system I wish to
analyse?” These form the basis for what we can term the postulates of quantum mechanics.

A postulate is a fundamental principle or, in a mathematical sense, an unproved statement that should be
taken for granted. The following is not an exhaustive list of postulates with regard to quantum mechanics,
but they are the important ones we need to be aware of at this stage. Remember, however, there is
strong evidence for all these postulates (maybe not mathematically, but then physically) so you can
regard this as near to the truth as modern science allows.

Postulate 1.
The state of a quantum mechanical system is completely specified by a function that depends on
a complete set of parameters that define that object. All possible information about the system can be
derived from Ψ ( x ) . This function, called a wavefunction, has the important property that Ψ ( x ) Ψ ( x )dx
∗

is the probability that the particle lies in the interval dx, located at x.
Postulate 2
To every observable in classical mechanics there corresponds an operator in quantum
mechanics

An example of this was the Hamiltonian for a free particle. Another useful one is the momentum operator,
which in one dimension is

∂
pˆ x = −ih
∂x

Postulate 3
In any measurement of the observable associated with the operator  , the only values that will
ever be observed are the eigenvalues a n , which satisfy the eigenvalue equation

Aˆ Ψn = a n Ψn

There are more postulates, but these nicely encapsulate our knowledge of quantum mechanics thus far
in the course.

It is worth bearing in mind that although it contains many weird ideas totally outside our normal everyday
experience, when quantum mechanics has been tested face to face with other understandings of nature
(intuition, special relativity etc) quantum mechanics has always been vindicated as the
accurate description of “how reality works”. I hope you have enjoyed, or at least you were intrigued, by
this trip into the subatomic world that seems so much at odds with our normal sense of “reality”.

Next year we will look at applying quantum mechanics to molecules and how it can
explain exactly what a chemical bond is, while in Level 3 we will see what quantum
mechanics can tell us about chemical reactions!

Key points in lecture 8

• An orbital is a hydrogenic wavefunction that approximates to the true wavefunction of the

individual electrons in a multi-electron atom.
• The energy of an individual electron is affected by the presence of other electrons in the atom.
These electron-electron correlations are very difficult to solve using quantum theory hence
quantitative predictions are not very accurate.
• By studying the radial probability distributions we can qualify the observed effects of electron
shielding and penetration that determine the energetic ordering of the atomic subshells.
• Two-electron wavefunctions are the antisymmetric and symmetric combinations of one-electron
(orbital) wavefunctions.
• The anti-symmetric two-electron wavefunction contains a Fermi-hole which minimises the
repulsive interactions between the electrons, lowering its energy versus its symmetric partner.

On the final page there is a very useful flow chart illustrating some of the connections between the
various concepts we have seen in the lectures: commit it to memory and have no fear in the exam!