Atomic Structure

and the Periodic

Table

Dimitri Mendeleev, 1834-1907

What distinguished Mendeleev was not only genius, but a passion for the elements.
They became his personal friends; he knew every quirk and detail of their behavior.

- J. Bronowski
Atomic Structure and
the Periodic Table

What if there’s more than one electron?

Helium: a nucleus with charge +2e and two electrons,

the two electrons repelling one another.

Cannot solve problems exactly with the Schrödinger equation

because of the complex potential interactions.

Can understand experimental results without computing the wave

functions of many-electron atoms with the help of approximation
methods.
Multi-electron atoms
When more than one electron is involved, the potential and the
wave function are functions of more than one position:

V  V (r1 , r2 ,..., rN )   (r1 , r2 ,..., rN , t )

Solving the Schrodinger Equation in this case can be very hard.

But we can approximate the solution as the product of single-
particle wave functions:

(r1 , r2 ,..., rN , t )  1 (r1 , t ) 2 (r2 , t )  N (rN , t )

It turns out that we’ll be able to approximate each i with a

Hydrogen wave function.
Quantum numbers
The four quantum number introduced for the H-atom can
be used for multi-electron atoms, too:
n: principal quantum number
ℓ: angular momentum quantum number
mℓ (or ℓz): magnetic quantum number (z-component of L)
ms (or σz): magnetic quantum number for the spin

allowed values of the quantum numbers:

n = 1, 2, 3, 4, . . .
ℓ = 0, 1, 2, 3, . . . , n − 1
mℓ = −ℓ, −ℓ + 1, . . . , 0, 1, . . . , ℓ − 1, ℓ
ms = −½, +½
 Notation for the values of the
quantum numbers
Principal quantum number:
n= 1 2 3 4 5...
Conventional notation: K L M N O...

Angular momentum quantum number:

ℓ= 0 1 2 3 4 5...
Conventional notation : s p d f g h...
Pauli Exclusion Principle
To understand atomic spectroscopic data, Pauli proposed his
exclusion principle:

No two electrons in an atom may have the same set of

quantum numbers (n, ℓ, mℓ, ms).

It applies to all particles of half-integer spin, called fermions. Electrons

and particles in the nucleus are fermions.

The periodic table can be understood by two rules:

Aufbau principle: The electrons in an atom tend to occupy the

lowest energy levels available to them.
The Pauli exclusion principle.
Pauli Exclusion Principle
On the example of an infinte square-well potential:

2-electron 3-electron 5-electron one possible

ground ground ground 3-electron
state state state excited state
Electronic
structure of
selected
atoms

Shell: all states for a given

n. For axample: K-shell, L-
shell, ...

Subshell: all states for given

n and ℓ. For example 1s, 2s, (ground (1st excited
2p, ... state) state)

Electronic structure is given

by listing the number of
electrons for each subshell.
Max. number of electrons on each
shell and subshell
Max. number of electrons on each
shell and subshell
Atomic Structure
How many electrons may be in each subshell?
Total
For each mℓ: two values of ms 2
For each ℓ: (2ℓ + 1) values of mℓ 2(2ℓ + 1)

Recall: ℓ = 0 1 2 3 4 5 …
letter = s p d f g h …
ℓ = 0, (s state) can have two electrons.
ℓ = 1, (p state) can have six electrons, and so on.

The lower ℓ values have more elliptical orbits than

the higher ℓ values.
Electrons with higher ℓ values are more
shielded from the nuclear charge.
Electrons with higher ℓ values lie higher in
energy than those with lower ℓ values.
4s fills before 3d.
Atomic structure
Hydrogen (H): (n, ℓ, mℓ, ms) = (1, 0, 0, ±½) in ground state.
In absence of external magnetic field the energies of the ms = ½ and ms
= −½ states are approx. equal.
Electron configuration: 1s1

Helium (He): 1st electron: (n, ℓ, mℓ, ms) = (1, 0, 0, ½),

2nd electron: (n, ℓ, mℓ, ms) =(1, 0, 0, −½).
Electron configuration: 1s2 (closed K shell)
Periodic
table
Groups and
Periods

Groups:
Vertical columns.
Same number of
electrons in an ℓ
orbit.
Can form similar
chemical bonds.

Periods:
Horizontal rows.
Correspond to filling
of the subshells.
Inert Gases: The Periodic
Last group of the periodic table Table
Closed p subshell except helium
Zero net spin and large ionization energy
Their atoms interact weakly with each other
Alkalis:
Single s electron outside an inner core
Easily form positive ions with a charge +1e
Lowest ionization energies
Electrical conductivity is relatively good
Alkaline Earths:
Two s electrons in outer subshell
Largest atomic radii
High electrical conductivity
 The Periodic
Halogens:
Table
Need one more electron to fill outermost subshell
Form strong ionic bonds with the alkalis
More stable configurations occur as the p subshell
is filled

Transition Metals:
Three rows of elements in which the 3d, 4d, and 5d
are being filled
Properties primarily determined by the s electrons,
rather than by the d subshell being filled
Have d-shell electrons with unpaired spins
As the d subshell is filled, the magnetic moments,
and the tendency for neighboring atoms to align
spins are reduced
Lanthanides (rare earths): The Periodic
Have the outside 6s2 subshell Table
completed
As occurs in the 3d subshell, the
electrons in the 4f subshell have
unpaired electrons that align
themselves
The large orbital angular momentum
contributes to the large
ferromagnetic effects

Actinides:
Inner subshells are being filled while
the 7s2 subshell is complete
Difficult to obtain chemical data
because they are all radioactive
Total Angular Momentum

Orbital angular momentum Spin angular momentum

Total angular momentum

L, Lz, S, Sz, J, and Jz are quantized.

Total Angular Momentum
If j and mj are quantum numbers for the single-electron hydrogen atom:

Quantization of the magnitudes:

The total angular momentum quantum number for the single electron
can only have the values
Spin-Orbit Coupling

An effect of the spins of the electron and the orbital angular

momentum interaction is called spin-orbit coupling.

The dipole potential energy

The spin magnetic moment 

is the magnetic field due to the electron’s orbital motion.

where a is the angle between .

Total Angular Momentum
Now the selection rules for a single-electron atom become

Δn = anything Δℓ = ±1
Δmj = 0, ±1 Δj = 0, ±1

Hydrogen energy-level diagram for

n = 2 and n = 3 with
spin-orbit
splitting.
Many-Electron Atoms
Hund’s rules:

The total spin angular momentum S should be maximized to the

extent possible without violating the Pauli exclusion principle.
Insofar as rule 1 is not violated, L should also be maximized.
For atoms having subshells less than half full, J should be minimized.

For a two-electron atom

There are LS coupling and jj coupling to combine four angular

momenta J.