Chapter 12

Quantum Mechanics
and Atomic Theory
Classical Physics
Classical mechanics
Maxwells theory of electricity,
magnetism and electro-magnetic
radiation
Thermodynamics
Kinetic theory

Eletromagnetic Radiation
Class radiation
Blackbody Radiation
Ultraviolet Catastrophe()
The classical theory of matter, which
assumes that matter can absorb or emit
any quantity of energy, predicts a
radiation profile that has no maximum
and goes to infinite intensity at very
short wavelengths.


1900J.W.RayleighJ.H.Jeans


Rayleigh-Jeans law


ultraviolet catastrophe
T k
c
B v
3
3
8tv
=

By combining the formulae of Wien and Rayleigh,
Planck announced in October 1900 a formula now
known as Planck's radiation formula.
Max Planck

1858~1947
Planck initiated the
study of quantum
mechanics when he
announced in 1900 his
theoretical research
into the radiation and
absorption of
heat/light by a black
body.
Max Plancks Theory

The Nobel Prize in Physics
1918

1
2
) (
3
3

=
kT
hv
e
v
c
h
v R
t
h: Plancks constant
k: Boltzmanns constant
C: speed of light
v: frequency of light
Plancks Impacts
In classical physics, energy is a
continuous variable.
Planck defined the amount of energy, a
quantum of energy, E=nhv
In quantum physics, the energy of a
system is quantized.
Albert Einstein
1879~1955
Einstein contributed more than
any other scientist to the
modern vision of physical
reality. His special and general
theories of relativity are still
regarded as the most
satisfactory model of the large-
scale universe that we have.
Photoelectric Effect
Albert Einstein,
The Nobel Prize in Physics 1921
KE
electron
=1/2mv
2
=hv-hv
0

hv: energy of incident photon
hv
0
: energy required to remove electron
from metals surface
The wave nature of electrons
Louis de Broglie,
The Nobel Prize in
Physics 1929


=h/mv
Light waves
Werner Heisenberg
1901~1976
Werner
Heisenberg did
important work in
Quantum
Mechanics as well
as nuclear physics.
Uncertainty Principle
Werner Karl Heisenberg
The Nobel Prize in Physics 1932




)
2
(
2 t
h
p x = > A A

The Atomic Spectrum
of Hydrogen
The Bohr Model
Niel Bohr
The Nobel Prize in Physics 1922

2
18
2
2.178 10 ( )
:
:
Z
E J
n
n integer
Z atomic number

=
The electron in a
hydrogen atom moves
around the nucleus only
in certain allowed
circular orbits.


Max Planck
Albert Einstein
Louis de Broglie
Werner Heisenberg

Niel Bohr

Quantum Mechanics
By the mid-1920s, Werner Karl
Heisenberg, Louis de Broglie and
Erwin Schrdinger developed the
wave mechanics or more commonly,
quantum mechanics.
Tunnel Effect
Quantum effect in biological systems
Rudolph A. Marcus was awarded the
1992 Nobel Prize in Chemistry.
Marcus theory
Electron transfer reactions
Schrdinger Equation
nvalue) nergy(eige E: total e
r an operato :Hamiltoni H
n) genfunctio orbital(ei ction for :wave fun
E H
equation eigenvalue

=
Particle in a box
m
k
E
mE
k
kx A
mE
kx A k
dx
kx A d
dx
x d
kx A x Suppose
h
x
mE
dx
x d
E
dx
d
m dx
d
m
H
V l energy) V(potentia energy) T(kinetic E
E H
2
2
) sin (
2
) sin (
) sin ( ) (
sin ) (
)
2
( ) (
2 ) (
) ( ) (
2 2

) 0 (

2 2
2
2
2
2
2
2
2
2
2 2
2
2
2 2
2
2 2

= =
= = =
=
= =
= =
= + =
=
t
Boundary Conditions
The particle cannot be outside the
box-it is bound inside the box.
In a given state the total probability
of finding the particle in the box
must be 1.
The wave function must be
continuous.
1 ) ( sin ) (
1. be must state given a in y probabilit
total The box. a in particle a finding of y probabilit
relative the means function wave the of square The
) sin( ) (
) sin( ) sin( ) ( 0 ) ( ) 0 (
) sin( ) (
and constant the define
0
2 2
0
2
= =
= = =
= = = =
=
} }
dx x
L
n
A dx x
x
L
n
A x
L
n
k n kL
n A kL A L L
kx A x
A k
L L
t
t t
t
t
) sin(
2
) (
)
2
(
8 2
) (
2

1
2
1
)
2
sin(
4
1
2
1
) ( sin
2 sin
4
1
2
1
sin

1
) ( sin
2
2 2
2 2
2
0
0
0
2
2
2
0
2
x
L
n
L
x
h
mL
h n
m
L
n
E
L
A
A
L x
L
n
L
n
x xdx
L
n
cx c x cxdx
A
dx x
L
n
n
L
L
L
L
t
t
t
t t t
t
=
= = =
=
= = =
=
=
}
}
}

Three energy levels

Three Dimension Box
z)
L
n
( y)
L
n
( x)
L
n
(
L L L
z) y (x
)
L
n
L
n
L
n
(
m
h
E
z
z
y
y
x
x
z y x
z
z
y
y
x
x
sin sin sin
8
, ,
8
2
2
2
2
2
2 2
=
+ + =
Degenercy

221 212 122

211 121 112

111
E
L
x
=L
y
=L
z
The spherical polar coordinate system
The Wave Function for the Hydrogen
Atom
) ( 10 178 . 2 )
8
(
) (

sin
1
cot
1 1 2
2

2
2
18
2
0
4
2
2
2
2
2 2 2 2
2
2 2
2 2
2
2
2
n
Z
J
h
me
n
Z
E
r
Ze
r V V
r r r r r r
T
r
Ze
V T H
E H
) R(r)(r)(
n

= =
= =
(

c
c
+
c
c
+
c
c
+
c
c
+
c
c
=
+ v = + =
=
=
c
| u u
u
u

The Physical Meaning of a Wave

Function
The square of the function evaluated at a
particular point in space indicates the
probability of finding an electron near that
point.

2
:probability distribution
dv: small volume element

2
1 1 1 1
2
2 2 2 2
[ ( , , )]
[ ( , , )]
r dv N
r dv N
u |
u |
+
=
+
The probability
distribution for the
hydrogen 1s orbital

Calculate the probability
at points along a line
drawn outward in any
direction from nucleus.
number of nodes=n-1
nodes
The radial probability
distribution for the
hydrogen 1s orbital
in spherical shell
Bohr radius: 0.529
Denoted by a
0
0.529
) 4 (
)
3
4
(
) (
2 2
3
2 2
r R
dr
r d
R
dr
dV
R t
t
= =
Relative Orbital Size
The normally accepted arbitrary
definition of the size of the hydrogen
1s orbital is the radius of the sphere
that encloses 90% of the total electron
probability.
For H(1s), r(1s)=2.6a
0
=1.4

Quantum Numbers
n: the principal quantum number

l: the angular momentum quantum
number

M
l
: the magnetic quantum number

Quantum Numbers
principal quantum number (n)
Have integral values (1,2,3)
I t is related to the size and energy of orbital.
As n increases, the orbital becomes larger and
the electron spends more time farther from the
nucleus
An increase in n also means higher energy
Quantum Numbers
angular momentum quantum number (l)
Have integral values from 0 to n-1.
Determines the shapes of the atomic orbital.


Value Letter Used
0 s
1 p
2 d
3 f
4 g
Quantum Numbers
magnetic quantum number (m
l
)
Have integral values between l and l,
including zero.
Relates to the orientation in space of
angular momentum associated with
the orbital.



2P
x
n value
l Value
Orientation in space
Electron Spin and Pauli Principle
electron spin quantum number (m
s
):
+1/2 and -1/2
Pauli Principle: In a given atom, no
two electrons can have the same set of
four quantum numbers (n, l, m
l
, m
s
)
Polyelectronic Atoms
the kinetic energy of the electrons as they
move around the nucleus
the potential energy of attraction between
the nucleus and the electrons
the potential energy of repulsion between
the two electrons
First ionization energy: 2372 kJ/mol
Second ionization energy: 5248 kJ/mol
Hydrogen Like Approximation
Z
eff
=Z
actual
-(effect of electron repulsions)
1<Z
eff
<2
Substituting Z
eff
in place of Z=1 in the hydrogen
wave mechanical equations

2+ e
-
e
-
Z
eff
+
e
-
Actual He atom
Hypothetical He atom
Valence electrons and Core
electrons
Valence electrons: the electrons in the outermost
principal quantum level of an atom.

Core electrons: inner electrons
Penetration effect
Core electrons
Na:1s
2
2s
2
2p
6
3s
1
K: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1

Aufbau principle
The physical and chemical properties of elements
is determined by the atomic structure.
The atomic structure is, in turn, determined by the
electrons and which shells, subshells and orbitals
they reside in.
The rules of placing electrons within shells is
known as the Aufbau principle.
As protons are added one by one to the nucleus
to build up the elements, electrons are similarly
added to these atomic orbitals.
Ionization Energy
X(g) X
+
(g)+e
-
The ionization energy for a particular electron
in an atom is a source of information about the
energy of the orbital it occupies in the atom.
Resulting ion will not reorganize in response to
the removal of an electron.
The ionization energies do provide information
that is quite useful in testing the orbital model
of the atom.
Ionization of Al
Al(g) Al
+
(g)+e
-
I
1
=580 kJ/mol

Al
+
(g) Al
+2
(g)+e
-
I
2
=1815 kJ/mol


Al
+2
(g) Al
+3
+e
-
I
3
=2740 kJ/mol


Al
+3
(g) Al
+4
+e
-
I
4
=11600 kJ/mol


(1) 1s
2
2s
2
2p
6
3s
2
3p
1
1s
2
2s
2
2p
6
3s
2
(2) 1s
2
2s
2
2p
6
3s
2
1s
2
2s
2
2p
6
3s
1
(3) 1s
2
2s
2
2p
6
3s
1
1s
2
2s
2
2p
6
(4) 1s
2
2s
2
2p
6
1s
2
2s
2
2p
5
The values of first ionization energy for
the elements in the first five periods.


As n increases, the size
of the orbital increases,
and the electron is easier
to remove.
The electron affinity for atoms among the first
20 elements that form stable, isolated X
-
ions.