Quantum Numbers to Periodic

Tables:
The Electronic Structure of Atoms

The electronic structure of atoms can be understood in

terms of the Schrödinger wave equation.

The Atom

Atomic nuclei are born naked, but their net positive

charge – their atomic number Z – attracts the
comparatively mass-less electrons to produce neutral
atoms:

 The tiny-but-dense nucleus of a gold atom,

atomic number Z = 79 so the Au79+ ion, attracts
79 negatively charged electrons to give a neutral
atom of gold, Au.

 Compared with the size of the gold nucleus, the

Au atom is huge... even compared with the
relative size of the Sun and our solar system:
The above diagram is developed from one on the HyperPhysics website but converted to
metric units.

The Electronic Structure of The Atom

The negatively charged electrons "associate" with the

positively charged nucleus as three dimensional
resonant standing waves:

The electrons move about the point positive charge

in a beautiful & subtle quantum mechanical dance

The modes of resonance for single electron systems

such as the hydrogen atom are described by the
Schrödinger wave equation. Very briefly Schrödinger:

 Knew of de Broglie's proposal that a moving

particle has wavelength, l, proportional to Plank's
 constant, h, and momentum p so that l = h/p, a
property we now known as wave-particle duality.
 So constructed a differential equation for a wave-
like electron resonating in three dimensions
about a point positive charge, the time-
independent Schrödinger wave eqn.
(Wikipedia):

 Solutions to the Schrödinger wave equation

correspond to modes of electron resonance and
are formally called wavefunctions.
 Wavefunctions assume discrete, or quantised,
energies and have energies which correspond to
the spectral lines of one electron atoms and ions
of the type: H•, He+, Li2+, Be3+, etc.
 Although not exactly the same, chemists tend to
call wavefunctions "orbitals".

1-Dimensional resonant standing waves, the

vibrating string:
2-Dimensional resonant standing wave, a vibrating
drum skin (see QuickTime movies here and here):
3-Dimensional resonant standing waves, atom
wavefunctions from the Schrödinger wave equation:

Quantum Numbers to Orbitals

Chemists recognise s, p, d and f-orbitals. The

topologies of these orbitals: the shape, phase &
electron occupancy are described by four quantum
numbers:

N The principal quantum number

The subsidiary or azimuthal or angular
L momentum or orbital shape quantum number

Ml The magnetic quantum number

Ms The electron spin quantum number
From Wikipedia:

These quantum numbers conspire to give spherical s-

orbitals, dumbbell shaped p-orbitals that come in sets of
three, double dumbbell d-orbitals that come in sets of
five, etc.:
Electrons enter and fill orbitals according to four rules:

Pauli Orbitals can contain a

Exclusion maximum of two electrons
Principal which must be of opposite
spin.
Aufbau or Electrons enter and fill lower
Build-up energy orbitals before higher
Principle energy orbitals.
Hund's Rule When there there are
degenerate (equal energy)
orbitals available, electrons will
enter the orbitals one-at-a-time
to maximise degeneracy, and
only when all the orbitals are
half filled will pairing-up occur.
This is the rule of maximum
 multiplicity.
Madelung's Orbitals fill with electrons as n
Rule + l, where n is the principal
quantum number and l is the
subsidiary quantum number.
This rule 'explains' why the 4s
orbital has a lower energy than
the 3d orbital, and it gives the
periodic table its characteristic
appearance.
Certain 'magic' numbers of electrons of electrons exhibit
energetic stability: 2, 10, 18, 36, 54, 86 and, one
assumes, 118, are associated with the Group 18 inert or
noble gases: He, Ne, Ar, Kr, Xe, Rn & Uuo.

 The 'magic' numbers inevitably arise from the

underlying quantum mechanics, but as Richard
Feynman told us (here): "I think I can safely say
that nobody understands quantum mechanics."

We can predict quantum mechanical patterns,

but we don't know why we can predict the
patterns. We do not understand QM in terms of
a deeper theory.

Now available on the web are Richard

Feynman's "Messenger Lectures" where he
looks at the nature of physical theory and its
relationship with mathematics. Highly
recommended!

Quantum Patterns

The pattern of orbital structure is very rich and can be

mapped onto the two dimensions of paper in many
different ways.

Some mappings emphasize how the orbitals are

ordered and filled with electrons, others stress how the
chemical elements and their orbitals are ordered with
respect to atomic number Z. Each tells us something
different about atomic orbital structure and/or elemental
periodicity.

Orbital Filling

Madelung's Rule says the orbitals fill in the order n + l

(lowest first). This gives the sequence:

 (n = 1) + (l = 0) = 1 1s
 (n = 2) + (l = 0) = 2 2s
 (n = 2) + (l = 1) = 3 2p
 (n = 3) + (l = 0) = 3 3s
 (n = 3) + (l = 1) = 4 3p
 (n = 4) + (l = 0) = 4 4s
 (n = 3) + (l = 1) = 4 3d
 (n = 4) + (l = 1) = 5 4p
 (n = 5) + (l = 0) = 5 5s
 and so on...
A nice electron shell representation from the
Encyclopedia Britannica:
Thus, the orbital filling sequence is, from the bottom of
this diagram, upwards because the lowest energies fill
first:
Electron Shells

As electrons are added, the quantum numbers build up

the orbitals. Read this diagram, from the top
downwards:
Elements by Orbital, And Some Subtleties...

The electronic structure can be illustrated adding

electrons to boxes (to represent orbitals). This
representation shows the Pauli exclusion principle, the
aufbau principle and Hund's rule in action.

There are some subtle effects with the d block elements

chromium, Cr, and copper, Cu. Hund's rule of maximum
multiplicity lowers the energy of the 3d orbital below that
of the the 4s orbital, due to the stabilisation achieved
with a complete and spherically symmetric set of five 3d
orbitals containing five or ten electrons. Thus,

 Chromium has the formulation: [Ar] 3d5 4s1 and

not: [Ar] 3d4 4s2
 Copper has the formulation: [Ar] 3d10 4s1 and not:
[Ar] 3d9 4s2