Chem 59-250

The Electronic Structure of Atoms

Classical Hydrogen-like atoms:
Atomic Scale: 10-10 m or 1
+

Proton mass : Electron mass

1836 : 1
Problems with classical interpretation:
- Should not be stable
(electron should spiral into nucleus)
- Atomic spectra wrong
(discrete lines instead of continuum)

Chem 59-250

Quantum Chemical Interpretation:

e- are best described by wave functions and quantum numbers.

Quantum means not continuous.

Quantum numbers for electrons:

n = principal quantum number

l = azimuthal quantum number
(orbital angular momentum)
ml = magnetic quantum number
ms = spin magnetic quantum number

Chem 59-250

Energy levels and n

Spectral transitions predicted by:

1
1
E h RH 2 2
nh
nl
where:

n l < nh

Chem 59-250

Bohr Model of the H atom

Z2
1
En R 2 R 2
n
n
R

2 2e 4
2
h
4

0
2

R = 13.6 eV

radius(n) = n2a0
a0 = Bohr radius = 0.529

= reduced mass (nucleus and electron)

Z = nuclear charge (1 for H)
e = charge of electron
0 = permittivity of a vacuum
h = Planks constant

Chem 59-250

n = principal Energy, Size SHELL

n = 1, 2, 3
n = 1 : ground state
n = 2 : first excited state
n = 3 : second excited state

1
E n 13.6 2
n
E1 = -13.6 eV
E2 = -3.40 eV

E3 = -1.51 eV
E4 = -0.85 eV

E5 = -0.54 eV

E = 0 eV

Chem 59-250
l = azimuthal, orbital angular momentum
degeneracy, shape SUBSHELL

l = 0, 1, 2 n 1

degeneracy = 2 l + 1

0 1 2 3 4, 5, 6

type

p d f g, h, i

degeneracy 1 3 5 7 9, 11, 13

s = sharp
p = principal
d = diffuse

Chem 59-250
ml = magnetic type, orientation in space ORBITAL
ml = 0, 1, 2 l

l
# of orbitals in a subshell = 2 l + 1

ml

orbital

0 s

0 pz
1 px
1 py

0 d2z2-x2 -y2 = dz2

1 dxz
1 dyz

2 dx2 y2
1s orbital

2 dxy

Chem 59-250

Wave functions and Orbitals

= wave function
2 = probability (electron) density
4r22 = radial distribution function

polar coordinates

E
H

= Rnl(r)Ylml(,)
Rnl(r) radial function
Ylml(,) angular function

Chem 59-250

Nodes: surfaces where there is 0 probability of finding an electron

Number of nodes = n - 1
Number of radial nodes = n - l 1
Number of angular nodes = l
0 for s orbitals
1 for p orbitals
2 for d orbitals (except dz2)

A website demonstrating nodes for 2D wavefunctions can be found at:

http://www.kettering.edu/~drussell/Demos/MembraneCircle/Circle.html

Chem 59-250

s orbitals

p orbitals

(the shading is backwards)

Chem 59-250

d orbitals

Chem 59-250
Summary of quantum numbers needed for H:

Z2
n Energy of shell: En R 2 , size: radius(n) = n2a0
n

l type (degeneracy) of subshell: s(1), p(3), d(5), f(7) .
ml type and orientation of orbitals in a subshell

Energy level diagram:

Chem 59-250

Many electron atoms

He, Z = 2

Z2
En R 2
n
22
E1 R 2
1
Predict: E1 = -54.4 eV
Actual: E1 = -24.6 eV

Something is wrong with the Bohr Model!

Chem 59-250
ms = spin magnetic electron spin
ms =

(- = ) (+ = )

Pauli exclusion principle:

Each electron must have a unique set of quantum numbers.
Two electrons in the same orbital must have opposite spins.

Electron spin is a purely quantum mechanical concept.

H

Chem 59-250

Energy level diagram for He. Electron configuration: 1s2

Energy

3
2

n
H

paramagnetic one (more) unpaired electrons

S

He

diamagnetic all paired electrons

Chem 59-250
Effective Nuclear Charge, Z*
The presence of other electrons around a nucleus screens
an electron from the full charge of the nucleus.
We can approximate the energy of the electrons by
modifying the Bohr equation to account for the lower
effective nuclear charge:

Z* = Z -

Z *2
En R 2
n

Z* is the effective nuclear charge

Z is the atomic number
is the shielding or screening constant

Chem 59-250

Helium , Z = 2
Predicted: E1 = -54.4 eV

Actual: E1 = -24.6 eV

Z *2
En R 2
n
Z*2
- 24.6 -13.6 2
1

Z*

24.6 12
13.6

Z* = 1.34

1.34 = 2 -
= 0.66

Chem 59-250

Lithium , Z = 3
Predicted: E2 = -30.6 eV

Actual: E2 = -5.4 eV

Z *2
En R 2
n
Z *2
-5.4 -13.6 2
2

Z*
-

5.4 22
13.6

Z* = 1.26

1.26 = 3 -
= 1.74

Chem 59-250
We want to be able to predict and Z*
Slaters rules for the prediction of for an electron:
1. Group electron configuration as follows:
(1s)(2s,2p)(3s,3p)(3d)(4s,4p)(4d)(4f)(5s,5p) etc.
2. Electrons to the right (in higher subshells and shells) of an electron do
not shield it.
3. If the electron of interest is an ns or np electron:
a) each other electron in the same group contributes 0.35 (0.30 for 1s)
b) each electron in an n-1 group contributes 0.85
c) each electron in an n-2 or lower group contributes 1.00
4. If the electron of interest is an nd or nf electron:
a) each other electron in the same group contributes 0.35
b) each electron in a lower group (to the left) contributes 1.00

Chem 59-250
Example with a valence electron on oxygen: O, Z = 8
Electron configuration: 1s2 2s2 2p4

a) (1s2) (2s2 2p4)

Z* = Z -

b) = (2 * 0.85) + (5 * 0.35) = 3.45

1s

2s,2p

Z* = Z -
Z* = 8 3.45 = 4.55

This electron is actually held with about 57% of the

force that one would expect for a +8 nucleus.

Chem 59-250
Example with two electrons for nickel: Ni, Z = 28
Electron configuration: 1s2 2s2 2p6 3s2 3p6 4s2 3d8

(1s2) (2s2 2p6) (3s2 3p6) (3d8) (4s2)

Z* = Z -

For a 3d electron:
= (18 * 1.00) + (7 * 0.35) = 20.45
1s,2s,2p,3s,3p

Z* = Z -

3d

Z* = 28 20.45 = 7.55

For a 4s electron:
= (10 * 1.00) + (16 * 0.85) + (1 * 0.35) = 23.95
1s,2s,2p

Z* = Z -

3s,3p,3d

4s

Z* = 28 23.95 = 4.05

Chem 59-250
The basis of Slaters rules for
s and p orbitals have better penetration to the nucleus than
d (or f) orbitals for any given value of n
i.e. there is a greater probability of s and p electrons being
near the nucleus

This means:

1. ns and np orbitals completely shield nd orbitals

2. (n-1) s and p orbitals dont completely shield n s and p orbitals

Chem 59-250 Periodicity of Effective Nuclear Charge

Z* on valence electrons
H
1.00
Li
1.30
Na
2.20
K
2.20
Rb
2.20
Cs
2.20

Be
1.95
Mg
2.85
Ca
2.85
Sr
2.85
Ba
2.85

B
2.60
Al
3.50
Ga
5.00
In
5.00
Tl
5.00

C
3.25
Si
4.15
Ge
5.65
Sn
5.65
Pb
5.65

N
3.90
P
4.80
As
6.30
Sb
6.30
Bi
6.30

O
4.55
S
5.45
Se
6.95
Te
6.95
Po
6.95

F
5.20
Cl
6.10
Br
7.60
I
7.60
At
7.60

He
1.65
Ne
5.85
Ar
6.75
Kr
8.25
Xe
8.25
Rn
8.25

Chem 59-250
Shielding and Effective Nuclear Charge
The energy of valence electrons in an atom/ion
changes with the loss of addition of an electron.
Slaters rules are only approximate and can give poor
predictions. For example:
They ignore the differences in penetration between s and p
orbitals. Real s and p orbitals do not have the same energy.
They assume that all electrons in lower shells shield outer
electrons equally effectively.

Z* can be used to estimate ionization energy:

Z *2
Hie 13.6 2
n

Chem 59-250
Shielding and Effective Nuclear Charge
Effective nuclear charge can be used to rationalize
properties such as the size of atoms and ions.

Cp*2Be

Cp*2B+

Be and B+ are isoelectronic (1s2 2s2) but very different

because of effective nuclear charge.