Chem 5

Chapter 10

The Periodic Table and Some

Atomic Properties

Part 3
November 6, 2002
Wave Function Ψ(x), Ψ(r,θ,φ)

Probability Density Ψ2(x), Ψ2(r,θ,φ)

Probability 1D Ψ2(x)dx, 3D Ψ2(r,θ,φ)dV

Screening

Penetration

Effective Nuclear Charge Zeff = Z - S

 At r =∞ E= 0

Orbital Energy Why En negative?

Z eff2
En = − RH
n2

Atom or Ion Radius

n=1
n=2
n=3
 1  l (l + 1)  
2
n a0 r
rnl = 1 + 1 − 2   n=4
Z eff  2  n 

n 2 a0
rn ∝
Z eff Not fixed orbits, but average r
 Total Energy E = Ek + V
mv 2 p 2
Ek = = ≥0
2 2m
high V1 Unbound and escaping
y1 “Pathfinder” E> 0
V Define V=0 at r→∞
0
y0 low V0 r
For a bound satellite
Potential energy with fixed orbit E< 0

V = mg y Need a reference point! Potential Energy

mM
Potential difference between two points V (r ) ∝ −
r
∆V = V1 –V0 = mg y1 - mg y0 = F ∆y dV mM
F= ∝ 2
dr r

Gravitational Potential r is the center to center distance

of the object and the earth, with
masses m and M respectively.
 V
Define V=0 at r→∞

r
Fixed Bohr orbits

Probability distributions of r
according to Schrödinger Eq.

Potential Energy E = Ek + V
E < 0 Bound
Ze • e E > 0 Unbound, like “Pathfinder”
V (r ) = −
r
For bound states
Total orbital energy is quantized
Z2
En = − RH 2
n
1
Columbic Potential En = Ek + V = V <0
2
 Zero Point Energy and Uncertainty Principle
The kinetic energy is Ek= <p2>/2m, p being the momentum of
the electron.

Probability Probability
Density for x ∆x Density for p ∆p
P(x) P(p)

x 0 p

Uncertainty Principle For the minimum Ek, <p>= 0

∆x ∆p >= h/4π Ek= <p2>/2m >0
This is the minimum kinetic energy
∆p = h/(4π∆x)
- Zero Point Energy
 V
Define V=0 at r→∞

With the Zero Point Energy,

Potential Energy Ek >0 even for the lowest E.

Ze • e The electron is not at rest at

V (r ) = − the nucleus.
r
We could estimate the Bohr
radius based on the
Uncertainty Principle
(Lecture notes 10-1).

Columbic Potential
 Ionization Energy

Na(g) → Na+(g) + e- I1=496kJ/mol

More generally, I.E. is the minimum energy needed to

remove an electron from the nth shell in a gaseous atom.

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

I = En
 Z eff2 Periodic trends
I = RH Increasing across period
n2
n=2 Decreasing down group
Noble gases high I.E.
Zeff
Alkali metals low I.E.
n=3

Zeff

n=2 n=3 n=4

Trends in First IE
Ionization Energy
Larger Zeff

Ionization Energy
Larger n

Z eff2
I = RH
n2
Arrow - Increasing
How to measure I.E.? Photoelectron Spectroscopy
p470
- Photoelectric effect applied not to
metals but to free atoms

Continuum
hv EkNe

I.E.

Kinetic Energy
analyzer

I.E. = - En = hv – Ek

Kinetic energy of the free electron (like the Pathfinder)

 Orbital Energies Measured by Photoelectron Spectroscopy

Z eff2
En ,l = − RH
n2

Experimental
Measurement of Zeff
 Electron Affinity
The energy change associated with the addition
of an electron to a gaseous atom.

Cl(g) + e– → Cl–(g) ∆E= -349 kJmol-1 Exothermic

Two definitions!

EA = ∆E the electron affinity is negative if ∆E<0.

EA = -∆E the electron affinity is positive if ∆E<0.

We use the first one.

 Electron Affinities Cl + eÆ Cl-
400 Z eff2
E = − RH 2 Cl
F n
300
Larger
-ELECTRON AFFINITY

Zeff
200 S
n from 3 to 4
C Si
O
100 H Li
Na
B Al P
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Zeff~0
He Be N Mg
-100
Ne Ar More repulsion
than attraction
-200
ATOMIC NUMBER

Tends to be more exothermic across period

Trends in Electron Affinities

Electron Affinity
More negative

Electron Affinity
More negative
Z eff2
E = − RH
n2

Arrow - Increasing
Cations are smaller than their corresponding
neutral atoms.
One less electron pulled in by nuclear charge

2 n=3
n
rn ∝ Smaller Zeff
Z eff

n=2
Larger Zeff
Anions are larger than their corresponding neutral
atoms.
Same Z and repulsion among electrons increases radius

Zeff is smaller for an anion.

n2
rn ∝
Z eff

The more negative charges, the bigger the ion

r(O) < r(O - ) < r(O 2 – )

 Increasing Ionic Radius

Zeff
Increasing Atomic Radius

Increasing Ionic Radius

n n2
rn ∝
Z eff

Increasing Atomic Radius

Is photoexcitation the only way to generate cations?

Of course not!

Where is the energy coming from?

Demo: The reaction of Na and Cl

2 Na ( s ) + Cl2 ( g ) 
→ 2 NaCl ( s )
Ionization Electron
Energy of Na Affinity of Cl

Columbic
Attraction