Chem 5

Chapter 10
The Periodic Table and Some
Atomic Properties
Part 2
November 4, 2002
Artificial Elements?
?
http://probability.ca/jeff/java/utday/
x
P(x)
∆x
Galton board
Probability Distribution
Define Probability Density, P(x)
such that Probability = P(x) ∆x
Probability is
- unitless
- proportional to ∆x
- equal to unity when integrated over
the whole range or space.
1 P(x)dx =

∞ −
Probability density is
- a continuous function of x
- has units of per unit distance (for 1D
distribution), per unit area (for 2D distribution)
or per unit volume (for 3D distribution )
Neither probability nor
probability density is
negative.
1-D Standing Wave
Tie the ends down
two nodes
o
+
-
y
x
one node
no node
Traveling wave
Not allowed
Ends not tied down
o
+
-
y
o
+
-
y
Waves with positive and negative amplitudes,
amplitude variation along x, and nodes
Particle in a Box
ψ
2
are the probability densities for
finding the particle, not probabilities!
Probability Distribution
of the Particle
p322
x 0
Solutions of Schrödinger Eq
n quantum No.
n – 1 nodes
0
x
1-D Schrödinger Equation
Eψ V(x)ψ
dx
ψ d
m 8π
h
2
2
2
2
= + −
p323
Potential Energy V(x) = 0, Total Energy E = V + E
k,
m particle mass

dx
ψ d
m 8π
h
2
2
2
2
= −
Verify the solutions
|
.
|

\
|
=
L
x n
L
x
n
π
ψ sin
2
) (
2
2 2
8mL
h n
E
n
=
n = 1, 2, 3 …
with
Left side
|
.
|

\
|
|
.
|

\
|
− = −
L
x n
L L
n π π
cos
dx
d 2
m 8π
h
dx
ψ d
m 8π
h
2
2
2
2
2
2
|
.
|

\
|
=
L
x n
L L
n
L
n π π π
sin
2
m 8π
h
2
2
|
.
|

\
|
=
L
x n
L L
n π
sin
2
8m
h
2
2 2
n n
E ψ =
right side
Energy levels for a particle in a box
• There are n-1 nodes in the nth wave
functions– same as in a H atom. The
more nodes, the higher the energy.
• Zero point energy. E=E
k
> 0 for the
lowest energy, n=1, which is a
consequence of the uncertainty principle.
• The energy spacing is inversely
proportional to L
2
.
• The energy is quantized.
2
2 2
8mL
h n
E
n
=
n=1
n=2
n=3
n=4
Work by Prof. Moungi Bowendi at MIT
Quantum dots - nanometer crystals of CdSe
The different colors of emission under ultraviolet illumination are due to
different diameters of the nanocrystals in different vials.
The size dependence of the emission frequency can be explained by
quantum mechanics of the particle (electron) in a box.
R
2
r
2
) , ( ) ( φ θ
lm nlm
Y r R
nl
= Ψ
Wave Function
) , ( ) (
2 2 2
φ θ
lm nlm
Y r R
nl
=
Fig. 9-32 of text, the vertical
axis should be R
2
r
2
, not 4πR
2
r
2
1-D Probability Density
3-D Prob. Density
Ψ
φ θ θ φ θ φ θ d drd r Y r R d Y r R d
lm nl lm nl
nlm
sin ) , ( ) ( V ) , ( ) ( V
2 2 2 2 2 2
= = Ψ
Probability in dV
R
2
(r)r
2
1-D Radial Probability Density Integrating over θ and φ
1D Prob. density
R
2
Y
2
(θ,φ)
3D Prob. density
R
R
2
r
2
0
Potential Energy
Potential Energy, V
Kinetic Energy, E
k
Total Energy, E
p222
low V
E = E
k
+ V
high V
Gravitational Potential
V linear with respect to height
Columbic Potential
e
-
+Z
dr
r dV
r
Ze
F
) (
2
2
= =
V V E E
k n
2
1
= + =
Total orbital
energy
2
2
n
Z
R E
H n
− =
V
r
V=0
r
Ze
r V
2
) ( − =
∞ → r
Potential Energy
r
V
p323
2
2
n
Z
R E
H n
− =
r
Columbic Attraction
Force
e - electron charge
R
H
Ryberg const
Screening (or Shielding) in Multi-electron Atoms
Screening reduces the apparent nuclear charge.
e
-
+Z +Z
e
-
Z
eff
= Z - S
Effective nuclear charge
Z
eff
approaches +1 Z
eff
approaches Z
r
e r Z
r V
eff
2
) (
) ( − =
Orbital Energy
n E
n
2
2
n
Z
R E
eff
H n
− =
Z
eff
E
n
Eq. 10.4
R
H
Ryberg Const
)
`
¹

+

¹
´
¦
+ >= =<
2
0
2
) 1 (
1
2
1
1
n
l l
Z
a n
r r
eff
nl
a
0
Eq. 10.5
n <r>
Z
eff
<r>
An example
F
-
, Na
+
,Mg
2+
are isoelectronic
What are relative sizes?
1s
2
2s
2
2p
6
eff
Z
n
r
2

Na
+
is 95 pm
Mg
2+
is 66 pm
F
-
is 133 pm
Same n
But different Z
Z
eff Mg2+
> Z
effNa+
> Z
effF-
H
-
(1s
2
)
Z
eff
= 1- 0.3 = 0.7
e
-
• Z=1

e
-

Z=2
e
-

e
-

He(1s
1
2p
1
)
Z
eff
~2-0=2
Z
eff
~2-1=1
eff
Z
n
r
2

Another Example of
e
-
• Z=1

H
Z=2
e
-

e
-

He(1s
2
)
Z
eff
= 2 – 0.2 =1.8
Penetration
- to circumvent screening
-The ability of electrons in s (compared to p) orbitals
or p (compared to d) orbitals to get close to nucleus
r
e r Z
r V
eff
2
) (
) ( − =
Potential energy
Z
eff2s
> Z
eff2p
E
2s
< E
2p
2
2 2
) (
2
1
) (
2
1
n
Z
R
r
e r Z
r V E
eff
H
eff
− = − = =
Total energy
R
2
r
2
Higher probability to be close, larger Z
eff
Compare E
2s
and E
2p
Compare E
3s
, E
3p,
E
3d
Higher probability to be close, large Z
eff
R
2
r
2
Z
eff3s
> Z
eff3p
> Z
eff3d
E
3s
< E
3p
< E
3d
Degenerate Energy cross over Energy splitting
Energy crossover is dependent on the atomic No. (different Z
eff
)
K M Mn n
2+
E
3d
< E
4s
E
4s
< E
3d
4f
10
5d
1
6s
2
4f
3
6s
2 4f
4
6s
2
4f
5
6s
2
4f
6
6s
2
4f
7
6s
2
5d first Exceptions
Normal filling
Ionization Energy
Mg(g) →Mg
+
(g) + e
-
I
1
=738kJ/mol
The energy needed to ionize a gaseous atom.
2
2
2
2
2
2
n
Z
R
Z
n
Z
R E E E I
eff
H
eff eff
H i f
=
|
|
.
|

\
|

− = − = ∆ =
2
2
n
Z
R E I
eff
H n
= =
Alkali metals low I.E.
Noble gases high I.E.
2
2
n
Z
R I
eff
H
=
Increasing across period
n=3
Z
eff
n=2
n=3