Achmad Rochliadi, Ph.D.

Program Studi Kimia

Institut Teknologi Bandung

The Structure of
Many-electron
Atoms

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KI 2141 - Struktur dan Ikatan Kimia

The orbital approximation

Interaction in many-electron atoms : (eg. 2 electron atoms)
electron-1 vs nuclei
electron-2 vs nuclei
electron-1 vs electron-2

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No analytical expression of many-electron atom for the
orbital wavefunction and energy can be given.
Schrodinger equation CANNOT be solved exactly for
many-electron atoms.
Approximation and numerical computation is use to solved
this.
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Justification of orbital approximation

The wavefunction of many-electron atom is a
complicated function of the coordinate of all the
electron
An orbital approximation is made by assuming that each
electron is occupying its own orbital

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Each individual orbital resemble the hydrogenic orbital.
The corresponding nuclear charge is modified due to
the presence of other electrons.

Justification of orbital approximation

The orbital approximation will be exact if there are no
interaction between electrons.
The complete Hamiltonian, with electron interaction.

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The helium atom

The orbital approximation express the electronic
structure of an atom by configuration, a statement of
its occupied orbitals. A ground state of a hydrogenic
atom consists of the single electron in a 1s orbital,
and its report as 1s1

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A He atom has two electrons. The forming the atom
by adding the electrons in succession to the orbitals
of the bare nucleus (of charge 2e-). The first
electron occupies a 1s hydrogenic orbital.
He have Z=2 so the orbital is more compact than in H
itself. The second electron joins the first in the 1s
orbital, so the electron configuration of the ground
state of He is 1s2
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The lithium atom

Lithium have Z = 3 and 3 electron. The first 2 electron
occupied 1s orbital.
Pauli exclusion principle
No more than two electrons may occupy any given orbital,
and if two do occupy one orbital, then their spins must be
paired.

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Electrons with paired spins, denoted , have zero net spin
angular momentum.

By total wavefunction including the spin of the

particles for two electrons (1,2).
The Pauli principle implies that it is a fact of
nature that for fermion the wavefunction
must change sign if we interchange the
labels 1 and 2 wherever they occur in the
function:
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The lithium atom

Possibilites of spin of the electron
= spin up, = spin down, (1) = electron 1, (2) = electron 2
Spin states as normalized linear combination.

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The total wavefunction of the system is therefore the product
of the orbital part and one of the four spin states:

pau
The Pauli principle : A wavefunction to be acceptable (for
electrons), it must change sign when the electrons are exchanged.
factor (1)(2) into (2)(1), which is the same, because the
order of multiplying the functions does not change the value of
the product. The same is true of (1)(2) and (1)(2).
Therefore, the first two overall products are not allowed, because
they do not change sign.

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Survive Pauli

The acceptable product wavefunction (1)(2)(1,2) can be

expressed as a determinant:

Any acceptable wavefunction for a closed-shell species can be

expressed as a Slater determinant, as such determinants are known.
In general, for N electrons in orbitals a, b

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Writing simplified Slater :

For lithium. In Li (Z=3), the third electron cannot enter the

1s orbital because that orbital is already full: we say the K shell is
complete and that the two electrons form a closed shell. Because a
similar closed shell is characteristic of the He atom, we denote it
[He]. The third electron is excluded from the K shell and must
occupy the next available orbital, which is one with n=2 and hence
belonging to the L shell.

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Question is which available orbital (2s orbital or a 2p orbital) is
going to be used for the 3rd electron [He]2s1or [He]2p1

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Penetrating and shielding

Due to coulombic repultion between

electron the 2s and 2p orbitals in
many-electron atom are not
degenerate.

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The effect coulombic, when averaged
over all the locations of the electron,
is to reduce the full charge of the
nucleus from Ze to Zeff e, the
effective nuclear charge.
We say that the electron experiences
a shielded nuclear charge, and the
difference between Zand Zeff is
called the shielding constant,:
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Energies of subshells :
s<p<d<f
(for same l)
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The building up principles

The Aufbau principles, (German for building up), the
rules of occupation for electron in the orbital of
atoms. The order of occupation is
Each orbital may accomodate up to 2 electrons.

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For carbon :

Electrons occupy different orbitals of a given subshell

before doubly occupying any one of them

Hunds maximum multiplicity rule:

An atom in its ground state adopts a configuration with the
greatest number of unpaired electrons
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Strong electron-electron repulsion in 3d
Orbital of Sc

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Self-consistent field orbitals

The Schrdinger equation for many-electron atoms is
solved numerically and iteratively until the solutions
are self-consistent.
The interaction of electron-electron repultion make the
Shrodinger equation hard to be solved. The potential
energy for the electrons is

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HF-SCF
Hartree-Fock Self-consistent field
For example to solve 1s2 2s2 2p6. For 1 electron in p
orbital. The schrodinger equation has the form of

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The first term on the left is the contribution of the kinetic
energy and the attraction of the electron to the nucleus, just
as in a hydrogenic atom.
The second term takes into account the potential energy of
the electron of interest due to the electrons in the other
occupied orbitals.
The third term is an exchange correctionthat takes into
account the spin correlation effects discussed earlier.

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The radial distribution

functions for the orbitals of
Na based on SCF
calculations. Note the
shell-like structure, with
the 3s orbital outside the
inner K and L shells.

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