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Electronic Structure
A Visual-Historical Approach
David A. Katz
Department of Chemistry
Pima Community College
Tucson, AZ U.S.A.
Voice: 520-206-6044 Email: dkatz@pima.edu
Web site: http://www.chymist.com
Theories of Matter
• The Greeks and Hindus appear to have developed
theories on matter.
• Most of the writings are attributed to the Greeks due to
the amount of recorded information that has survived to
the present.
• Greeks thought substances could be converted or
transformed into other forms.
• They observed the changing of states due to heat and
equated it with biological processes.
• The Greeks were philosophers and thinkers, not
experimentalists, so they did not conduct experiments to
verify their ideas.
• Thales of Miletus (about 624-about 527 B.C.)
– Proposed that water is the primal matter from which
everything originated.
– He is also credited with defining a soul as that which
possesses eternal motion.
• Anaximander (610-546 B.C.)
– The primary substance, the apeiron, was eternal and
unlimited in extension. It was not composed of any known
elements and it possessed eternal motion (i.e., a soul).
• Anaximenes (585-524 B.C.)
– Stated that air is the primary substance
– Suggested it could be transformed into other substances
by thinning (fire) or thickening (wind, clouds, rain, hail,
earth, rock).
• Heraclitus of Ephesus (544-484 B.C.)
– fire is the primeval substance
– Change is the only reality.
• The Pythagoreans (Pythagoras (570-490 B.C.))
– Reduced the theory of matter to a mathematical and
geometric basis by using geometric solids to represent the
basic elements:
• cube = earth
• octahedron = air
• tetrahedron = fire
• icosahedron = water
• dodecahedron = ether
• Julius Plücker
(1801-1868)
– Evacuated tube
glowed, 1859
– Rays affected by a
magnet
• Johann Wilhelm Hittorf (1824-1914)
– Maltese cross tube, 1869
• Rays travel in straight line
• Cast shadows of objects
• William Crookes (1832-1919)
– Verified previous observations, 1879
– Caused pinwheel to turn
• Composed of particles
– Have negative charge
• Joseph John Thomson (1846-1940)
e/m = -1.759 x 108 coulomb/gram - 1897
• Robert Millikan (1868-1923)
– Oil drop experiment – 1909
e = -1.602 x 10-19 coulomb
N = 6.062 x 1023 molecules/g-molecule
Pieces of Atoms – the proton
• Eugen Goldstein (1850-1930)
– Canal rays - 1886
Pieces of Atoms – the neutron
• James Chadwick (1891-1974)
Discovered the neutron – 1932
The Subatomic Particles
electron
0
1 e or e -1.602 x 10-19 9.109 x 10-28 -1 0.0005486 ≈ 0
A. M. Mayer
“We suppose that the atom consists of a
number of corpuscles moving about in a
sphere of uniform positive
electrification…
when the corpuscles are constrained to
move in one plane …the corpuscles will
arrange themselves in a series of
concentric rings.
When the corpuscles are not constrained
to one plane, but can move about in all
directions, they will arrange themselves in
a series of concentric shells”
J. J. Thomson, 1904
Photo Reference: Bartosz A. Grzybowski,
Howard A. Stone and George M. Whitesides,
Dynamic self-assembly of magnetized,
millimetre-sized objects rotating at a liquid–air
interface, Nature 405, 1033-1036 (29 June 2000)
Ernest Rutherford (1871-1937)
Hans Geiger and Ernest Marsden – 1908
Barium
platinocyanide
Henri Becquerel (1852-1908)
Radiation activity, 1896
Uranium nitrate
pitchblende
Radium bromide
Marie Curie with inset photo
of Pierre Curie
Ernest Rutherford (1871-1937)
α, β, γ - 1903
As the temperature
decreases, the peak of the
black-body radiation curve
moves to lower intensities
and longer wavelengths.
The Quantum Mechanical Model
• Albert Einstein (1879-1955)
The photoelectric effect – 1905
Planck’s equation: e = hν
Equation for light : c = λν
c
Rearrange to
hc
Substitute into Planck’s equation e
From general relativity: e = mc2
Substitute for e and solve for λ
h
mc
Light is composed of particles called photons
The Bohr Model - 1913
• Niels Bohr (1885-1962)
The Bohr Model – Bohr’s Postulates
1. Spectral lines are produced by atoms one at a
time
2. A single electron is responsible for each line
3. The Rutherford nuclear atom is the correct
model
4. The quantum laws apply to jumps between
different states characterized by discrete values
of angular momentum and energy
The Bohr Model – Bohr’s Postulates
5. The Angular momentum is given by
h n = an integer: 1, 2, 3, …
p n
2
( ) h = Planck’s constant
Paschen Series
Brackett Series
Pfund Series
Humphrey’s Series
The Bohr Model
The energy absorbed or emitted
from the process of an electron
transition can be calculated by the
equation:
1 1
E RH ( 2
2
n2 n1
)
where
RH = the Rydberg constant, 2.18 10−18 J,
and
n1 and n2 are the initial and final energy
levels of the electron.
The Wave Nature of the Electron
• In 1924, Louis de Broglie (1892-1987)
postulated that if light can act as a particle,
then a particle might have wave properties
• De Broglie took Einstein’s equation
h
mc
and rewrote it as
h
mv
where m = mass of an electron
v = velocity of an electron
The Wave Nature of the Electron
• Clinton Davisson (1881-1958 ) and
Lester Germer (1886-1971)
– Electron waves - 1927
• Werner Heisenberg (1901-1976)
– The Uncertainty Principle, 1927
“The more precisely the position is
determined, the less precisely the
x p
4
h
1 p principal
2 d diffuse
3 f fine
Looking at Quantum Numbers:
The Magnetic Quantum Number, ml
• Describes the orientation of an orbital with respect to a
magnetic field
• This translates as the three-dimensional orientation of
the orbital.
• Values of ml are integers ranging from -l to l:
−l ≤ ml ≤ l.
Values of l Values of ml Orbital Number of
designation orbitals
0 0 s 1
1 -1, 0, +1 p 3
2 -2, -1, 0, +1, +2 d 5
3 -3, -2, -1, 0, +1, +2, +3 f 7
Quantum Numbers and Subshells
• Orbitals with the same value of n form a shell
• Different orbital types within a shell are called subshells.
Pictures of s and p orbitals