Chem 5

Chapter 10

The Periodic Table and Some

Atomic Properties

Part 2

November 4, 2002
Artificial Elements?

?
 Galton board
Probability Distribution
http://probability.ca/jeff/java/utday/

Define Probability Density, P(x)

such that Probability = P(x) ∆x

Probability is P(x)
- unitless
- proportional to ∆x
- equal to unity when integrated over
the whole range or space. ∞
∫ P(x)dx = 1
−∞ x
∆x
Probability density is
- a continuous function of x
Neither probability nor
- has units of per unit distance (for 1D
probability density is
distribution), per unit area (for 2D distribution)
negative.
or per unit volume (for 3D distribution )
 1-D Standing Wave
Tie the ends down

two nodes
+
yo Not allowed
-
one node
+
yo
-
no node Traveling wave
+
yo
-

x Ends not tied down

Waves with positive and negative amplitudes,

amplitude variation along x, and nodes
 Probability Distribution
Particle in a Box of the Particle

n quantum No.
n – 1 nodes
x
0 0 x

p322
ψ2 are the probability densities for
Solutions of Schrödinger Eq finding the particle, not probabilities!
 1-D Schrödinger Equation

h 2 d 2ψ
− 2 2
+ V(x)ψ = Eψ p323
8π m dx
Total Energy E = V + Ek, m particle mass Potential Energy V(x) = 0,

h 2 d 2ψ
− 2 2
= Eψ
8π m dx
Verify the solutions
h2 d2ψ h 2 nπ 2 d   nπ x  
Left side − 2 =− 2
2  nπx  8π m dx 2
 cos 
ψ n ( x) = sin   8π m L L dx   L  
L  L  h 2 nπ nπ 2  nπ x 
= 2 sin  
8π m L L L  L 
n = 1, 2, 3 … h2 n2 2  n πx 
= sin  
8m L2 L  L 
n2h2
with En = = Enψ n right side
8mL2
 Energy levels for a particle in a box

• The energy is quantized.

n=4 • There are n-1 nodes in the nth wave

functions– same as in a H atom. The
more nodes, the higher the energy.
n=3
• Zero point energy. E=Ek > 0 for the
lowest energy, n=1, which is a
n=2
consequence of the uncertainty principle.
n=1
• The energy spacing is inversely
n2h2 proportional to L2.
En =
8mL2
 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.
 Radial probability distribution
Fig. 9-32 of text, the vertical
1-D Probability Density axis should be R2r2, not 4πR2r2
R2r2

Ψ
Wave Function nlm = R nl
( r )Ylm (θ , φ ) Ψ 2
3-D Prob. Density nlm = R 2
( r )Ylm (θ , φ )
2
nl

Probability in dV Ψnlm dV = R nl ( r )Y lm (θ , φ )dV = R nl ( r )Y lm (θ , φ ) r sin θdrdθdφ

2 2 2 2 2 2

Integrating over θ and φ 1-D Radial Probability Density R2(r)r2

 R2Y2(θ,φ)
3D Prob. density

R
Radial wave function

0
R2r2

1D Prob. density
 Potential Energy
Potential Energy, V

Kinetic Energy, Ek

p222 Total Energy, E

E = Ek + V
high V

Gravitational Potential
low V
V linear with respect to height
Columbic Potential V
V=0 r→∞

e- r

r Z2
En = − RH 2
n

+Z Potential Energy
Ze 2
V (r ) = −
r
p323
r V

Columbic Attraction
Total orbital En = Ek + V = 1 V
energy 2
Ze2 dV ( r )
Force F= 2 =
r dr Z2
En = − RH 2
e - electron charge n RH Ryberg const
Screening (or Shielding) in Multi-electron Atoms
Screening reduces the apparent nuclear charge.

e-

+Z +Z

e-

Effective nuclear charge Zeff = Z - S

Zeff approaches +1 Zeff approaches Z

Z eff (r )e 2
V (r ) = −
r
Orbital Energy
n En
Z eff2
En = − RH 2 Zeff En
n Eq. 10.4
RH Ryberg Const

Atom or Ion Radius

n 2 a0  1  l (l + 1)  
rnl =< r >= 1 + 1 − 2   a0 Bohr radius
Z eff  2  n 
Eq. 10.5

n <r>

Zeff <r>
 An example

F-, Na+,Mg2+ are isoelectronic 1s22s22p6

What are relative sizes?

n2
r ∝ Mg2+ is 66 pm
Z eff

Same n Na+ is 95 pm
But different Z F- is 133 pm
Z eff Mg2+ > Z effNa+ > Z effF-
 e-
Another Example of n 2 • H- (1s2)
Screening and Atomic Radii r ∝
Z eff
• Z=1
• e-
H •
Zeff = 1- 0.3 = 0.7
• Z=1

•
e-

Z=2
He(1s2) •
• e-
Zeff~2-0=2

e-
Z=2 •
•
•
e -

Zeff = 2 – 0.2 =1.8 e- •

Zeff~2-1=1
He(1s12p1)
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
Compare E2s and E2p
Higher probability to be close, larger Zeff

R2r2

Z eff ( r )e 2
Potential energy V (r) = −
r 2 2
Total energy 1 1 Z eff ( r )e Z eff
E = V (r) = − = − RH 2
2 2 r n
Zeff2s > Zeff2p E2s < E2p
Compare E3s, E3p, E3d

Higher probability to be close, large Zeff

R2r2

Zeff3s > Zeff3p> Zeff3d E3s < E3p < E3d

Degenerate Energy splitting Energy cross over
 Energy crossover is dependent on the atomic No. (different Zeff)

K Mn Mn2+

E4s < E3d E3d < E4s

4f105d16s2

4f36s2 4f46s2 4f56s2 4f66s2 4f76s2

5d first Exceptions Normal filling

 Ionization Energy

Mg(g) → Mg+(g) + e- I1=738kJ/mol

The energy needed to ionize a gaseous atom.

 Z eff
2 2
Z eff  2
Z eff
I = ∆E = E f − Ei = RH  2 − 2  = RH 2
 n ∞  n

Z eff2
I = En = RH
n2
 Z eff2
I = RH 2 Increasing across period
n
n=2 Noble gases high I.E.

Alkali metals low I.E.

n=3

Zeff

n=3