CHAPTER 6:

ELECTRONIC STRUCTURE

The Nature of Light
Quantized Energy/Photons
Photoelectric Effect
Bohrs Model of Hydrogen
Wave Behavior of Matter
Uncertainty Principle
Quantum Mechanics/Atomic Orbitals
Quantum Numbers/Orbitals

Representations of Orbitals
Many-Electron Atoms
Effective Nuclear Charge
Relative Energies of Orbitals
Electron Spin/Pauli Excl. Principle
Electron Configurations
Periodic Relationships

Wave Nature of Light
Electromagnetic Radiation
electric & magnetic components with
periodic oscillations
length in m, cm, mm, mm, nm, l
frequency in cycles/sec or hertz, n
nl = c where c = speed of light
long wavelength
short wavelength
Quantized Energy and Photons
Black Body Radiation
heated bodies radiate light and l depends
on temperature
Planck -- energy released in packets
smallest packet is a quantum
energy of one quantum , E = hn
h, Plancks constant = 6.63 x 10
- 34
J-s
Practice Ex. 6.2:
A laser that emits light in short pulses has a
n = 4.69 x 10
14
s
-1

and deposits 1.3 x 10
-2
J of
energy during each pulse. How many quanta
of energy does each pulse deposit?
E = hn
E of 1 quantum = (6.63 x 10
-34
J-s)

(4.69 x 10
14
s
-1
)
= 3.11 x 10
-19
J/quanta

1.3 x 10
-2
J = 4.2 x 10
16
quanta
3.11 x 10
-19
J/quanta
Photoelectric Effect
metals exposed to light, radiant energy, emit
electrons
each metal has a minimum n of light
Einsteins photons of light must have sufficient
threshold energy
energy of photon depends on the n of light, E = hn
high frequency, short wavelength (l = c/n) high
energy
light is also quantized, 1 photon = 1 quanta
metal surface
photon with
E > threshold
e
-
with kinetic energy =
photon E - threshold E
e
-
Bohrs Model of the Hydrogen Atom
Line Spectra
spectrum -- light composed of different wavelengths
and energies
contiunous spectrum -- continuous range of ls and Es
line spectrum -- non-continuous spectrum (only specific
ls and Es)
Balmer 1800s n = C (1/2
2
- 1/n
2
)
n = 3, 4, 5, 6 C = 3.29 x 10
15
s
- 1

400 450 500 550 600
Hydrogen Line Spectrum
Bohrs Model

electrons in orbits around nucleus
orbits are allowed energies which are quantized
to move between quantized orbits, electrons must
either absorb or emit quanta of energy
E = - R
H
( 1/n
2
) n = 1, 2, 3, 4 . . . . .
principle quantum number
R
H
(Rydberg constant) = 2.18 x 10
-18
J
e
-
e
-
nucleus
n=1 n=2 n=3 n=4
e
-
Energy
absorption
nucleus
e
-
e
-
n=1 n=2 n=3 n=4
Energy
emission
e
-
e
-
nucleus
n=1 n=2 n=3 n=4
DE
1

DE
2

DE
3

DE = E
f
- E
i
= hn
DE
1
> DE
2
> DE
3

energy of the transition depends on the levels

DE = E
f
- E
i
= hn or DE = n = E
f
- E
i

h
n = (R
H
/ h )(1/n
i
2
- 1/n
f
2
)

or DE = R
H
(1/n
i
2
- 1/n
f
2
)

n
i
= initial level of electron

n
f
= final level of electron
DE or n is +
radiant energy absorbed
nucleus
n=1 n=2 n=3 n=4
DE or n is -
radiant energy
emitted
n=1 2 3 4 5 6
Balmer Series - visible
H line spectrum
H
Lyman Series
- in the uv
Wave Behavior of Matter
Basis for Quantum Mechanics
De Broglie wave equation
l = h matter waves
mv

Uncertainty Principle -- Werner
Heisenberg
fundamental limitation on how precisely we
can know the location and momentum
Quantum Mechanics and Atomic Orbitals
Quantum Mechanics or Wave Mechanics
mathematical method of predicting the behavior
of electrons
wave functions are solutions to these
mathematical equations
wave functions predict the probability of
finding electron density, Y
2

wavefunction describes orbitals
Orbitals & Quantum Numbers

orbitals describe volumes of electron density
orbitals are of different types s, p, d, f
each orbital is described by a set of quantum
numbers n, l, m
each quantum number has an allowed set of values
Quantum Numbers
n can have values of 1, 2, 3, 4, 5 . . . .
describes the major shell or distance from the nucleus
l can have values of 0, 1, 2, 3 . . . n-1
describes the type of subshell
l = 0 s subshell l = 1 p subshell
l = 2 d subshell l = 3 f subshell
m can have values of - l . . . 0 . . . + l
describes which orbital within the subshell
n=1 n=2
nucleus
+
s
s
p
p
p
s
p
p
p
d
d
d
d
d
s
p
p
p
d
d
d
d
d
f
f
f
f
f
f
f
n=4 n=3
s
p
d
f
l = 0
l = 1
l = 2
l = 3
total number of orbitals in a subshell is n
2

maximum number of electrons in a subshell is 2n
2

maximum number of electrons in an orbital is 2
s last quantum number describes the spin
on an
electron
each electron has a spin + or -
n=1 n=2
nucleus
+
s
s
p
p
p
s
p
p
p
d
d
d
d
d
s
p
p
p
d
d
d
d
d
f
f
f
f
f
f
f
n=4 n=3
s
p
d
f
l = 0
l = 1
l = 2
l = 3
-1
0
+1
-2
-1
0
+1
+2
-2
-3
-1
0
+1
+2
+3
0
m
m
m
m
Orbital Pictures
s-type orbitals
always one orbital in the subshell with l = 0
and m = 0
are spherical
differences between s orbitals in different
major shells (with different n values)
size
remember, were talking in terms of
probability of the occurrence of electron
density
Notice that we are looking at a volume of diffuse electron
electron density as pictured by the many small dots
s orbital
cross-
sections
p-type orbitals
always three orbitals in the subshell with l = 1
and m = -1, 0, +1
are dumb-bell shaped
different m values are oriented along different
axes, x, y, or z (p
x
, p
y
, p
z
)
differences between p orbitals in different major
shells
size
d-type orbitals
always five orbitals in the subshell with l = 2 and
m = -2, -1, 0 +1, +2
most are four-lobed
different m values are oriented differently on x,
y, z axes d
z
2
, d
x
2
-y
2
, d
xy
, d
xz
, d
yz

differences between d orbitals in different major
shells
size
E
n
e
r
g
y

s
s
p p p
s
d d d d d
d d d d d f f f f f f f
p p p
Orbital/Subshell
energy levels in
the hydrogen atom
n=1
s
p p p
n=2
n=3
n=4
Multi-electron Atoms
screening effect
inner electrons shield the nuclear charge from
outer electrons
energy levels of subshells within major shells
become different
nuclear charge experience by outer electrons is
decreased
Z
eff
= Z - S
Z
eff
decreases with increasing l value
E
n
e
r
g
y

s
Orbital/Subshell
energy levels in
multi electron
atoms
n=1
s
p p p
n=2
s
n=3
n=2
p p p
n=3
d d d d d
n=3
Pauli Exclusion Principle
no two electrons can have the same exact set of
quantum numbers
consider this orbital and its two electrons





quantum numbers are n = 2, l = 1, m = 0
the two electrons must have a quantum number
that is different -- s = + and -
First electron has spin + and second electron -
p p p
n=2
l = 1 m = -1 0 +1
Electron Configurations
There is a pattern in the energy levels that hold
electrons
electrons fill up the pattern from the lowest
energy to the highest energy level
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s

for
1
H for
2
He
1s 1s

3
Li
4
Be
1s 2s 1s 2s
Hunds Rule
electrons enter degenerate orbitals in a subshell
one at a time until the subshell is half-filled

5
B
6
C
1s 2s 2p 1s 2s 2p

7
N
1s 2s 2p

8
O
1s 2s 2p
Periods 1, 2 & 3

3
Li


1s 2s

11
Na
1s 2s 2p 3s

19
K
1s 2s 2p 3s 3p 4s

outer shell is called the valence shell
Group 1

3
Li


1s 2s

11
Na
1s 2s 2p 3s

19
K
1s 2s 2p 3s 3p 4s

[Ne]
[Ne] 3s
1

[Ar]
[Ar] 4s
1

all group I elements have electron configuration
[nobel gas] ns
1


all group II elements have electron configuration
[nobel gas] ns
2


all group III elements have electron configuration
[nobel gas] ns
2
np
1


group IV elements
[nobel gas] ns
2
np
2


group V elements
[novel gas] ns
2
np
3
etc.
1 2 3 4 5 6 7 8
s
1
s
2
p
3
p
4
p
5
p
6
p
7
p
8
1
2
3
4
5
6
7
d
1
. . . . . . . . . . . . . . d
10
Electron Configuration & Periodic Table
ns
1

ns
2

ns
2
p
1
ns
2
p
2
ns
2
p
3
ns
2
p
4
ns
2
p
5

ns
2
p
6

ns
2
(n-1)d
1-10