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Lecture 5
Read textbook sections 7.1, 7.2

Last lecture
  2 sketch or interpret a plot of a
simplified wavefunction and relate it to n
   Quantum numbers
 First 3 quantum numbers  atomic orbital
 n = 1, 2, 3, 4 … (integers starting with 1)
 ℓ = 0, 1, 2, …(n – 1)
 mℓ = – ℓ, (– ℓ + 1), …, 0, …, ℓ

© M. Reid, Department of Chemistry, University of Alberta (2019)

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Fourth quantum number, ms

Spin quantum number
1 1
ms = – (or spin down) , (or spin
up) 2 2
An e– has magnetic properties
Electrons with the same spin – parallel spin.
Electrons with different spins – opposite spin.

© M. Reid, Department of Chemistry, University of Alberta (2019)

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Pauli’s exclusion principle (1925)
No two electrons in an atom can have the same
four quantum numbers.

Immediate implications:
• Max 2 e– in an orbital.
• e– 's within the same atomic orbital must have
opposite spins.

So the maximum number of electrons possible in

subshell
One s orbital 1 x 2 e– = 2 e–
Combined three p orbitals 3 x 2 e– = 6 e–
Combined five d orbitals 5 x 2 e– = 10 e–
Combined seven f orbitals 7 x 2 e– = 14 e–

© M. Reid, Department of Chemistry, University of Alberta (2019)

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Many-electron Atoms
One-electron (hydrogen-like) species can be treated exactly by the
Schrödinger equation. However, in atoms containing more than
one electron (many-electron species), the presence of electron-
electron repulsions causes the energy of the orbitals to vary in a
complicated way.
One-electron atom Many electron atom
(e.g., H atom) (e.g., He atom)

© M. Reid, Department of Chemistry, University of Alberta (2019)

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Many-electron Atoms
e–s are not all at the same distance r from the nucleus.

We must consider
 Kinetic energy of the e–
 Attractive potential energy between nucleus and e–
 Repulsive potential energy between e–

Need to make approximations for repulsive forces.

Outermost e– feels:
• Attraction from +ve nucleus
• Repulsion by other e– so that this e– is somewhat
screened or shielded from nucleus by the other e–.

© M. Reid, Department of Chemistry, University of Alberta (2019)

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The effect of the nuclear charge
The higher the nuclear charge the greater pull on the
electrons. That means that the energy is lowered (note
the negative scale) and that the system is more
stable.

© M. Reid, Department of Chemistry, University of Alberta (2019)

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Shielding: The effect of electron repulsions
Each electron also feels repulsions from other
electrons. Inner electrons (1s in diagram) prevent the
outer electron (2s in example) from experiencing
the full attraction of the nucleus, making its
removal somewhat easier (than expected).
This is called shielding or screening.

© M. Reid, Department of Chemistry, University of Alberta (2019)

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Net effect:
 Instead of Z, the e– feels an effective nuclear
charge, Zeff
 The effective nuclear charge is smaller
than the one felt by an inner e–
2

 Energy levels are different En  –

Ze
Which e– are more effective at screening? ff

n 2
 Obviously from previous page (fig. 7.3), the inner
electrons shield outer electrons better than
electrons in the same orbital.
Radial probability distribution

© M. Reid, Department of Chemistry, University of Alberta (2019)

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Recap:

1. Greater nuclear charge orbital energy.

2. Electron-electron repulsions orbital energy.
3.Electrons in outer orbitals (higher n) are shielded from the full nuclear
charge, so they have energy.
4.Orbitals with good penetration (having electron density close to the
nucleus) have energy.
Radial probability distribution curves help explain the difference in
penetration between different orbitals.
In general, for orbitals in the same shell:
(more shielding, more penetrating) s > p > d > f (less shielding, less penetrating)
(lower energy) (higher energy)

© M. Reid, Department of Chemistry, University of Alberta (2019)