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Chem 5

Chapter 10

The Periodic Table and Some


Atomic Properties

Part 1
November 1, 2002
“If you had only one sentence to
describe the most important scientific
knowledge we posses, what would
that sentence be? The answer is,
everything is made of atoms! ”

- Richard Feynman
Joseph Wright of Derby (1734-97)

The Alchemist in Search


of the Philosopher’s Stone
Discovers Phosphorus
(1771)
Modern physicists have accomplished one of the
goals of alchemy: the production of artificial gold.

“In 1980, a group of researchers at Lawrence Berkeley


Laboratory (Glen T. Seaborg, et. al.) reported the
production of a few billion atoms of gold…. A bismuth
target was bombarded with a ‘relativistic projectile’ that
chipped some protons from the Bi nuclei, forming gold.
The experiment produced less than one-billionth of a cent
worth of gold.”

From Adept Alchemy (Chapter 2) by Robert A. Nelson.


Cavendish Laboratory, Cambridge, UK
Periodic Table

When the elements are


arranged in order of
increasing atomic mass or
number, certain sets of
properties recur periodically.

Mendeleev (1834-1907)
The explanation of periodic table was the Holy Grail of the
early 20th century, one of the triumphs of quantum mechanics.
Quantum mechanics is the most successful theory in the history
of science, providing a quantitative understanding of the microscopic world.

Time line of the birth of quantum mechanics:


• 1900 Planck Quantization of energy for blackbody radiation
• 1905 Einstein Photoelectric effect
• 1913 Bohr Bohr model for hydrogen

• 1923 de Broglie Particle-wave duality


• 1924 Bose, Einstein Bose-Einstein statistics
• 1925 Pauli Pauli exclusion principle
• 1925 Heisenberg Matrix mechanics
• 1925 Schrödinger Schrödinger eq.
• 1926 Born Probability interpretation of wavefunctions
• 1926 Fermi, Dirac Fermi-Dirac statistics
• 1927 Heisenberg Uncertainty principle
• 1928 Dirac Relativistic wave equation and quantum field
theory
What is the diameter of the electron in a H atom?

Your text book assumes 10-14m – and that is wrong!

What is the approximate size of the wave function?

Uncertainty Principle ∆x∆p ≥ h / 4π

The electron cannot be still.

Minimum p2 ∆p 2 h2
Kinetic Ek = = =
2m 2m 2ma02
Energy

Zero-point energy
Bohr orbits of H atom
Estimating the Atomic Radius
h
Uncertainty Principle Æ The smallest radius a0 = ∆x ≈
∆p
Minimum p2 ∆p 2 2
h2 Potential Energy V = − e
Kinetic Ek = = =
Energy 2m 2m 2ma02 a0
h2 e2
Total Energy E = Ek + V = 2
− 2
2ma0 a0
dE h2 e2
For minimum E =− 3
+ 2 =0
da0 2ma0 a0

h 2
e2
a0 = 2
= 0.53 A = 53 pM E=− = −2.179 ×10 −18 J
me 2 a0

Bohr radius
What is the size of a nucleus?

Less than one thousandth of the diameter of an atom

According to the Uncertainty Principle

∆x∆p ≥ h / 4π , p ~ ∆p ∆x p

Why don’t the protons and neutrons fall apart?


Because of the strong interaction!
There are three kinds of forces in the universe:
Gravitational, electromagnetic, and strong interactions.

Electromagnetic interaction is sufficient for understanding chemistry.


Bohr radius Radial probability distributions
Similar to Fig. 9-32 in the text, but y axis not 4πR2(r)r2

R nl2 ( r ) r 2
Z / a0

r
a0 / Z
ψ 1s 2
Probability Density

ψ 1s 2 dv =
R nl2 (r )Ylm2 (θ , φ )r 2 sin θdrdθdφ

Probability
n 2 a0  1  l (l + 1)  
rnl = 1 + 1 − 2 
Z  2  n 
Screening in Multi-electron Atoms
Shielding reduces the apparent nuclear charge.

Effective Charge H- •e
-

Zeff = Z - S
• Z=1


e- •
H Zeff = 1- 0.3=0.7
• Z=1
He

•e
-
e-

Zeff = 1.0 Z=2

e-
Zeff = 2 - 0.2=1.8
Screening in the excited state of He 1s13p1
0.6

0.5 Is
0.4
Radial R2(r) r2
Probability 0.3
3p
Distributions 0.2

0.1

0
0 5 10 15 20 25 30
r (in a0)

What is the Zeff for 1s ?


Zeff= Z – S ~ 2 – 0 = 2 The 1s close to the nucleus, not screened
by 3p
What is the Zeff for 3p ?
Zeff= Z - S ~ 2 - 1 = 1 The 3p far away from the nucleus, well
screened by 1s
This He 3p orbital is like an H-atom 3p!
Penetration - The ability to circumvent screening

In a multi-electron atom, compare E2s and E2p

Z eff (r )e 2
V (r ) ∝ −
2
R nl ( r ) r 2
r
Z / a0
Z eff (r )e 2 Z eff (r ) e 2
V (r ) ∝ − ≠−
r r

Large contribution from small r and large Zeff(r)

Z eff2
En = − RH
n2
r
a0 / Z Zeff(s) > Zeff(p) E s < Ep
Penetration
In a multi-electron atom, compare E3s,E3p, E3d

0.25
3s Zeff(s) > Zeff(p) > Zeff(d)
0.2

0.15 3p
R 2 r2
0.1

0.05 3d
0
0 5 10 15 20 25 30
r (in a0)

2
Zeff
E n = −R H 2 Es < Ep < Ed
n
For multi-electron Atoms 2
Zeff
E n = −R H 2
n
Energy splitting within the same n

Ens<Enp<End<Enf

Energy crossover for different n e2

E4s<E3d

E5s<E4d

E6s<E4f <E5d<E6p

E7s<E5f <E6d<E7p
For certain but not all atomic No.
Electron Configuration and the Periodic Table
The essence of periodicity is that elements in the same
group of the table have similar electronic configurations.
The Aufbau Process
1. Minimizing energy
2. Paul exclusion principle
3. Hund’s rule

Periodic Properties:
Atomic radii
Inonic radii
Ionization energies
Electron affinities
Chemical reactivity
Interaction of Electromagnetic Waves with Matter

Electromagnetic spectrum
Mechanisms for color generation
What gives rise to a rainbow?

Dispersion
- Light velocity is
frequency dependent.

Why does your credit card give rainbow


colors? Diffraction
- A grating has
a periodic structure
at the dimension of the
light wavelength.

Why is the solution blue? Absorption


Scattering
Why is the sky blue or red?
Rayleigh Scattering

- Elastic scattering has higher efficiency


at higher frequencies

Mie Scattering
Why is the church glass
- Scattering by metallic particles
so colorful?

Raman Scattering
- Inelastic scattering, characteristic of
molecular vibrations
Southwark Cathedral, London,
where John Harvard was baptized in 1607.

What substance in the church glass gives


rise to these colors?

Mie scattering by
gold particles of
different diameters
What do you see from the lamps? Emission
Spontaneous Emission (Fluorescence)

Blackbody Radiation
LASER Emission

http://home.achilles.net/~jtalbot/data/elements/ The Noble Gases

Greek Argos –The lazy one

William Ramsay
1852-1916
Summary of Electromagnetic
Interactions with Matter
• Dispersion
• Diffraction
• Scattering
• Rayleigh scattering
• Mie scattering
• Raman scattering
• Absorption
• Emission
• Fluorescence
• Blackbody radiation
• Laser
Cecilia Payne-Gaposchkin (1900-1979)
In 1923, Cecilia Payne came to Harvard as a graduate
student from England. As an undergraduate, she had
heard lectures by Bohr and Rutherford that interested her
in astrophysics. At that time, however, the best an
educated woman could hope to do was to teach high
school.
Harvard College Observatory had a vast amount of
spectroscopic data. Every star has many spectral
lines. Different spectra among stars seemed to
suggest different stars’ compositions. Her thesis project
was to figure out what the spectral lines meant.
She found that the spectral lines have the same
frequencies but different intensities. She realized that the
compositions of the stars are the same; the only
difference is their temperatures. She was not only able to
determine the temperatures of the stars, but also came to
the conclusion that most stars are composed of hydrogen
and helium.
At first, her thesis committee did not believe her conclusions, but before long they
and other scientists hailed her work as the greatest thesis in astrophysics. She
later became the first woman professor at Harvard.
Star emission spectrum

Ca Absorption line of Ca

Calcium
energy levels

Boltzman distribution Hydrogen


energy levels
− E/k B T
Prob ∝ e
Abundance of Elements in the Universe and on the Earth