Multielectron atoms

◆ The Schrödinger equation can in principle be

applied to multielectron atoms
- however, it can only be solved approximately
◆ The orbitals derived from the Shrödinger equation
for the hydrogen atom are used for multielectron
atoms with a correction to take into account the
different effective nuclear charge
Electron spin
◆ The solutions of the Shrödinger equation for the hydrogen atom
are characterized (labeled) by the quantum numbers n, l and ml
– this is not enough to give agreement with experiment
– Stern and Gerlach showed that a beam of silver atoms splits into two
components on passing through a magnetic field
» can be explained by introducing the idea of electron spin
◆ A fourth quantum number, ms, the spin quantum number had to
be introduced
– ms can either be +1/2 or -1/2
◆ Electron spin comes naturally out of more sophisticated theory
than the Shrödinger equation
– the Dirac equation. This takes into account relativity.
Stern-Gerlach experiment
◆ If electrons do not have spin
beam of silver atoms should
not split
– silver [Kr]4d105s1
◆ Beam splits into two
component corresponding
to ms = +1/2 and ms =-1/2
The Pauli exclusion principle
◆ No two electrons in an atom can have the
same quantum numbers n, l, ml, and ms
– this means that an orbital can never have more
than two electrons in it
The Aufbau or filling principle
◆ In multielectron
atoms, the electrons
fill up the available
energy levels
(orbitals) starting
with the lowest
available level
The modern periodic table
Orbital energies
◆ The orbitals in a multielectron atom do not
have the same size or energy as the
corresponding orbitals in a hydrogen atom
– this is because the electrons in them experience
an effective nuclear charge (Zeff) that is
different from 1 (one)
Effective nuclear charge
◆ Each electron is attracted to the nucleus and
repelled by all the other electrons
– rather than thinking about all the individual attractive
and repulsive interactions it is simpler to consider the
attraction as being reduced by all the repulsions
» the electron experiences an effective nuclear charge Zeff which
is less than the real nuclear charge

electron with

attraction
charge -e Zeff = Z - σ
repulsion
σ is a shielding constant
nucleus with electron with
charge +Ze attraction charge -e
Shielding
◆ The value of the shielding constant and hence the
effective nuclear charge experienced by a given
electron depends on which orbitals are occupied
Effective nuclear charge
Z 1s 2s 2p
1 (H) 1.0
2 (He) 1.69
RDFs for 3 (Li) 2.69 1.28
lithium 4 (Be) 3.68 1.91
5 (B) 4.68 2.58 2.42
6 (C) 5.67 3.22 3.14
7 (N) 6.66 3.85 3.83
8 (O) 7.66 4.49 4.45
9 (F) 8.65 5.13 5.10
10 (Ne) 9.64 5.76 5.76
Penetration
◆ For an element such as potassium the 4s orbital
is more penetrating than the 3d orbitals as it has
maxima inside the core orbitals

4πr2ψ2

r
Variation of orbital energy with Z

◆ Orbital energies do not

always vary smoothly with
atomic number as they
depend on what other
orbitals are occupied
– they also vary with ion
charge. This plot only applies
for neutral atoms!
Hunds rule
◆ There is often more than one way of arranging
electrons within a set of degenerate orbitals
– they do not all have the same energy
– the lowest energy arrangement has the maximum
number of spin parallel electrons
» this is Hund’s rule of maximum multiplicity

Configuration (a) has the lowest energy

Hunds rule and carbon

◆ The three different

arrangements of 2p
electrons for carbon
differ significantly in
energy (~10,000 cm-1)
– this is ~ 120 kJmol-1
Three different
arrangements of roughly 1/4 the strength
electrons in 2p
orbitals
of an O-H bond in water
Electron configurations for atoms

◆ Some atoms do not have

the electron configuration
you would expect based on
the Aufbau principle
– Cr [Ar]4s13d5
– Cu [Ar]4s13d10
Electron configurations for ions
◆ Ease of removal of an electron often does
not mirror the filling order embodied in the
Aufbau principle
– Mn [Ar] 4s23d5 but Mn2+ [Ar] 4s03d5 not [Ar] 4s23d3
» this maters as the two configurations have different properties
• different colors and magnetic behavior
– this is not a unique example
» all transition metal atom loose their ns electron before their
(n-1) d electrons