1

***Test Dates: Syllabus on

CLEW***
Test Dates: There will be no make-up
tests or exams!

Test 1:October 4 - during class time
Test 2: November 6 - during class time
Final Exam: Saturday, Dec. 13, 12:00
2
Atomic Structure
The hydrogen atom, wavefunctions
and orbitals, many electron atoms,
spin, Slaters rules and effective
nuclear charge.
3
Lecture 1, lets start at
1
H!
Hydrogen economy old news?

4
Making and Moving H
2

Nearly all made from
hydrocarbons
Most used on site





Ways of the future
make for good media
coverage Well see
5
Start out with a Big Bang

Universe is 75% hydrogen and 23% helium. Irony?
Has been since about since about 3 minutes after big bang
Surprised? Not really reflected by Earths composition.
BIG
BANG
proton (p
+
)
neutron (n)
and
electron (e
-
)
soup

n + p
+

2
H
+
Deuterium
n +
2
D
+

3
H
+
Tritium
p
+
+
2
D
+

3
He
2+
3-Helium
2
D +
2
D
4
He
2+
3
H
+
+ p
+

4
He
2+
3
He
2+
+ n
4
He
2+
4-Helium

6
Abundance of Elements
7
Stars at Work
Our sun is young, and too small to make heavy nuclei
Big old stars convert He to larger nuclei
At around Fe, these processes are no longer favourable
Our solar system is recycled stardust.
p
+
+ p
+

2
H
+
e
+
u
e
2
H
+
+ p
+

3
He
2+
3
He
2+
+
3
He
2+

4
He
2+
+ 2 p
+

YOUNG STARS
3
4
He
12
C
BIGGER STARS
etc up to
56
Fe
Quantum Prep:Particle in a box
States defined by a
single quantum
number n.
Energy is never
zero
Energy depends
on n
2

8
9
Back to Hydrogen
Expt: Ionize H
2
into H atoms.
Populate excited states and
watch emissions.
This is in the visible region
What is the pattern?
(nm)
656 red
486 blue-green
434 blue
410 violet
397 ultraviolet
|
|
.
|

\
|

=
2 2
2
2
56 . 364
m
m

Where m is an integer > 2.

Balmer series (1855)
10
Bohr Model 1.
Rydberg, 1890, slightly
different presentation to
Balmer
|
|
.
|

\
|
9 = =
2 2
1 1
m n
hv E
H
Bohr found
Balmers/Rydbergs
numerical solution in 1913,
and arrived at a planetary
model
Bohr was well aware of the issues; a circulating electron
should emit radiation and spiral into nucleus.
11
Bohr Model 2.
Bohrs wild guess: certain
orbits are stable - restrict
angular momentum L.
Can equate electrostatic
attraction to centrifugal
force to figure out more
about these orbits.

|
.
|

\
|
= =
t 2
h
n mvr L
De Broglie would later interpret this as a
standing wave condition for an electron
(1923 thesis lead to Nobel Prize)

m = electron mass
v = electron velocity
r = radius of orbit
n = principle quantum number
Z = nuclear charge
E
Z
n
R
n
R
n
=
|
\

|
.
|
|
=
|
\

|
.
|
|
2
2 2
1
radius(n) = n
2
a
0
a
0
= Bohr radius
= 0.529
( )
R
e
=
2
4
2 4
0
2
2
t
tc h
= 13.6 eV
12

H+ + = E
+ = R
nl
(r)Y
lml
(u,|)

R
nl
(r) radial function

Y
lml
(u,|) angular function
polar coordinates
+ = wave function
+
2
= probability (electron) density
3-D: Wave functions and
Orbitals (Hydrogen 1925)
13
The Solution to the Hydrogen Atom
Schrodinger Equation
Three quantum numbers describe the
orbitals that are essentially standing wave
solutions

n = principle quantum number (1, 2, 3, 4)
l = orbital quantum number (0, 1, 2 n-1)
m
l
= magnetic quantum number (values
between l and +l )

n comes strictly from radial component of
function, and is analogous to Bohrs model
The l and m
l
quantum numbers come from
the angular components of the function
14
Principle Quantum Number (n)
Determines energy of orbital
NOTE: Only true for hydrogen;
energy of 2s =2p, etc.
n = 1, 2, 3
n = 1 : ground state
n = 2 : first excited state
n = 3 : second excited state

E
n
n
=
|
\

|
.
|
|
13 6
1
2
.
E
1
= -13.6 eV

E
2
= -3.40 eV

E
3
= -1.51 eV

E
4
= -0.85 eV

E
5
= -0.54 eV



E

= 0 eV
15
0
-500
-1000
-1500
E
n
e
r
g
y

(
k
J
/
m
o
l
)
1s
2s
3s
4s
2p
3p
4p
3d
4d
4f
Quantum Number l
l = azimuthal, orbital angular momentum
degeneracy, shape SUBSHELL
l = 0, 1, 2 n 1 degeneracy = 2 l + 1
Degenerate states have the same energy
l 0 1 2 3 4, 5, 6
type s p d f g, h, i
degeneracy 1 3 5 7 9, 11, 13
s = sharp
p = principal
d = diffuse
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m
l
= magnetic type, orientation in space
m
l
= 0, 1, 2 l

# of orbitals in a subshell = 2 l + 1
Magnetic Quantum Number (m
l
)
l m
l
orbital
0 0 s
1 0 p
z
1 p
x
1 p
y
2 0 d
2z
2
-x
2
-y
2 = d
z
2
1 d
xz

1 d
yz
2 d
x
2
y
2
2 d
xy
2p orbitals
y
x
z
y
x
z
y
x
z
p
x
p
y
p
z
17
The 1s Orbital
n = 1, l = 0, m
l
= 0
No nodes
18
The 2s and 3s Orbitals: Nodes
n = 2, l = 0, m
l
= 0
n = 3, l = 0, m
l
= 0


Number of nodes = n 1
Number of radial nodes = n l 1
Number of angular nodes = l
Nodes are surfaces where the values of the function is zero
The s orbitals only have radial nodes
19
The p Orbitals
n = 2, l = 1, m
l
= -1,0,+1
Has one node through
nucleus (2p)
y
x
z
y
x
z
y
x
z
p
x
p
y
p
z
20
The 3p Orbital
n = 3, l = 1, m
l
= -1, 0, +1
Seems like 3 nodes, but
actually 2 (n-1 = 2)
1 radial, 1 angular node

21
3d
z
2
z-axis is blue
The 3d Orbitals
n = 3, l = 2,
m
l
= -2,-1, 0, +1, +2
4 look the same, 1
looks different (d
z
2)
2 nodes (n-1)=2

z
x
y
z
x
y
z
x
y
d
xz
d
z
2 d
x
2
-y
2
z
x
y
d
xy
z
x
y
d
yz
3d
xz

y-axis is green
22
Many Electron Atoms
Something is wrong with our model!

+
-
-
E
Z
n
R
n
=
|
\

|
.
|
|
2
2
E
1
1
=
|
\

|
.
|
|
R
2
2
2
He, Z = 2
Predict: E
1
= -54.4 eV

Actual: E
1
= -24.6 eV
23
Electron spin (m
s
)
m
s
= spin electron spin
m
s
= (- = o) (+ = |)
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.
N
S
H
24
Energy Level Diagram for He.
Electron Configuration: 1s
2


N
S
H
N
S
He
paramagnetic one (more) unpaired electrons
diamagnetic all paired electrons
E
n
e
r
g
y

1
2
3
0 1 2
n
l
25
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:
E
Z
n
R
n
=
|
\

|
.
|
|
*2
2
Z* = Z - o

Z* is the effective nuclear charge
Z is the atomic number
o is the shielding or screening constant
26
Helium Z = 2
Predicted: E
1
= -54.4 eV

Actual: E
1
= -24.6 eV
- 24.6 -13.6
1
2
2
=
|
\

|
.
|
|
Z*
Z*
.
.
=
24 6 1
13 6
2
Z* = 1.34
1.34 = 2 - o
o = 0.66
+
- -
E
Z
n
R
n
=
|
\

|
.
|
|
*
2
2
27
Lithium Z = 3
Predicted: E
2
= -30.6 eV

Actual: E
2
= -5.4 eV
-5.4 -13.6
2
2
2
=
|
\

|
.
|
|
Z*
Z*
.
.
=
54 2
136
2
Z* = 1.26
1.26 = 3 - o
o = 1.74
+
-
-
-
E
Z
n
R
n
=
|
\

|
.
|
|
*
2
2
28
Predicting o and Z*
Slaters rules for the prediction of o 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

29
Example: Oxygen Valence Shell
Z* = Z - o
O, Z = 8
Electron configuration: 1s
2
2s
2
2p
4

a) (1s
2
) (2s
2
2p
4
)

b) o = (2 * 0.85) + (5 * 0.35) = 3.45
1s 2s,2p
Z* = Z - o

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.

30
Example with Two Electrons for
Nickel:
Z* = Z - o
Ni, Z = 28
Electron configuration: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
8

(1s
2
) (2s
2
2p
6
) (3s
2
3p
6
) (3d
8
) (4s
2
)

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

Z* = Z - o Z* = 28 20.45 = 7.55

For a 4s electron:
o = (10 * 1.00) + (16 * 0.85) + (1 * 0.35) = 23.95
1s,2s,2p 3s,3p,3d 4s

Z* = Z - o Z* = 28 23.95 = 4.05
31
The basis of Slaters rules for o
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


32
Z* on valence electrons

For the elements shown here, the effective nuclear
charge on the valence electrons never exceeds 8.25,
despite nuclear charges up to 86 (radon)!
H
1.00
He
1.65
Li
1.30
Na
2.20
K
2.20
Rb
2.20
Cs
2.20
Ba
2.85
Sr
2.85
Ca
2.85
Mg
2.85
Be
1.95
B
2.60
Al
3.50
Ga
5.00
In
5.00
Tl
5.00
Pb
5.65
Sn
5.65
Ge
5.65
Si
4.15
C
3.25
N
3.90
P
4.80
As
6.30
Sb
6.30
Bi
6.30
Po
6.95
Te
6.95
Se
6.95
S
5.45
O
4.55
F
5.20
Cl
6.10
Br
7.60
I
7.60
At
7.60
Rn
8.25
Xe
8.25
Kr
8.25
Ar
6.75
Ne
5.85
33
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
(except H).

They assume that all electrons in lower shells shield outer
electrons equally effectively.

Z* can be used to estimate ionization energy:
AH 13.6
ie
2
2
=
|
\

|
.
|
|
Z*
n
34
Summary
4 quantum numbers describe orbitals: n, l , m
l
,
m
s

The s, p and d-orbitals, nodes, radial
distribution function, degeneracy

Effective nuclear charge and Slaters rules

NEXT LECTURE: Hunds rules, trends: atomic
radii, ionization enthalpy

35
What is an eV? Good question.
A single atom is such a small thing that to talk
about its energy in joules would be inconvenient.
But instead of taking a definite unit in the same
system, like 10
20
J, [physicists] have unfortunately
chosen, arbitrarily, a funny unit called an
electronvolt (eV) ... I am sorry that we do that, but
that's the way it is for the physicists.

Richard Feynman, in a 1961 recorded lecture.
1eV = 1.60217653(14)10
19
joules
An electron volt is the kinetic energy gained by an electron
when it is accelerated through an electrostatic potential of 1 V.