Hydrogen / Helium

KE
PE: attraction

PE: repulsion

Electron Correlation Problem

Since the electron pathways are unknown, the
electron repulsions cannot be calculated
exactly. The Schrdinger equation that
results cannot be solved exactly. (p81, 2)
The electron correlation problem occurs with
all polyelectronic atoms. (p81, 3)

Approximation
To treat these systems using the quantum
mechanical model, we must make
approximations. (p81, 3)
The approximation used is to treat each
electron as if it were moving in a field of
charge that is the net result of the nuclear
attraction and the average repulsions of all
the other electrons. (p81, 3)

Attractions vs. Repulsions

Shielding

Shielding Effect

shielding effect

p81, 6

Orbital Energy Levels

Hydrogen: All the orbitals
in a given principal
quantum level have the
same energy (degenerate).
Polyelectronic atoms
Ens < Enp < End < Enf
Why??

Orbital Energy Levels

in Polyelectronic Atoms
When electrons are placed in a particular
quantum level, they prefer the orbitals in
the order s, p, d, and then f. (p81, r2)

2s vs. 2p Orbital in Polyelectronic Atoms

p81, Figure 2.21

Node

2s vs. 2p Orbital in Polyelectronic Atoms

The 2p orbital has its maximum probability
closer to the nucleus than for the 2s. This
might lead us to predict that the 2p would be
lower energy than the 2s orbital. (p81, r2)
The small hump of electron density that
occurs in the 2s profile very near the nucleus.
It spends a small but very significant amount
of time very near the nucleus. (p81, r2)

10

Penetration Effect

This penetration effect causes an electron in

a 2s orbital to be attracted to the nucleus more
strongly than an electron in a 2p orbital.
E2s < E2p in polyelectronic atom. (p81, r2)

11

Penetration Effect
p81, Figure 2.22(b)

E3s < E3p < E3d (p82, 2)

12

Penetration Effect
In general, the more effectively an orbital
allows its electron to penetrate the shielding
electrons to be close to the nuclear charge,
the lower the energy of that orbital. (p82, 3)

13