Chem 16 General Chemistry 1

02 Quantum Theory and Atomic Structures

Dr. Gil C. Claudio

Second Semester 2014-2015
Table of Contents

Contents
1 The Wave and Particle Nature of Light

2 Atomic Spectra

3 Wave-Particle Duality of Matter and Energy

4 Quantum Mechanical Model of the Atom

5 Quantum Numbers and Atomic Orbitals

5.1 The Four Quantum Numbers . . . .
5.2 Atomic Orbitals . . . . . . . . . . . .
5.3 Multielectron Atoms . . . . . . . . .
5.4 Electron Configurations . . . . . . .

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References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffy D. Madura, and Carey Bisonnette.
Quantum Chemistry 2nd ed by Donald A. McQuarrie.

1 The Wave and Particle Nature of Light

Limitations of the Planetary Model
The planetary model of the atom proposed by Rutherford had two
significant shortcomings.
1. Unlike planets orbiting a sun, electrons are charged particles. An
accelerating electric charge is known to emit electromagnetic waves.
An orbiting charge should steadily lose energy and spiral toward the
nucleus, colliding with it in a small fraction of a second.
2. The planetary model could not explain the highly peaked emission and
absorption spectra of atoms that were observed.

Electromagnetic Radiation
Electromagnetic radiation is a form of energy propagated as mutually
perpendicular electric and magnetic fields. It includes visible light, infrared,
ultraviolet, X ray, and radio waves.
A wave is a disturbance that transmits energy through a medium.
Amplitude is the height of the crest of a wave above the center line of the
wave.
The wavelength is the distance between successive crests or troughs of a
wave motion. Designated by .
The frequency of a wave motion is the number of wave crests or troughs
that pass through a given point in a unit of time. It is expressed by the
unit time1 (e.g., s1 , also called a hertz, Hz).
Electromagnetic Spectrum

en.wikipedia.org/wiki/File:Light dispersion of a mercury-vapor lamp with a flint glass prism IPNr0125.jpg

en.wikipedia.org/wiki/File:Electromagnetic-Spectrum.png

Speed of Light
A distinctive feature of electromagnetic radiation is its constant speed of in
a vacuum, often referred to as the speed of light.
c =
EXAMPLE: Most of the light from a sodium vapor lamp has a wavelength of
589 nm. This corresponds to a frequency of 5.09 1014 Hz
2

Constructive Interference
In phase

Destructive Interference
Out of phase

2 Atomic Spectra

en.wikipedia.org/wiki/File:Linear visible spectrum.svg

Emission spectrum of Hydrogen

410 nm 434 nm

486 nm

656 nm

commons.wikimedia.org/wiki/File:Emission spectrum-H labeled.svg

Emission spectrum of Iron

en.wikipedia.org/wiki/File:Emission spectrum-Fe.svg

750

620

590

570

495

450

380

Emission Spectra of Elements

Continuous emission spectrum

Blackbody Radiation and Classical Physics

A blackbody is one that absorbs and emits all frequencies.
As temperature T increases, the frequency of emitted light also
increases.
Spectral distribution of the intensity of blackbody radiation as a function
of frequency. Increase in temperature shifts the maximum to higher
frequencies.
Classical physics was unable to explain the distribution of frequencies.
Blackbody Radiation and Max Planck
The first person to offer a successful explanation of blackbody radiation
was Max Planck (1900).
He assumed that the radiation emitted by the body was due to the
oscillations of the electrons in the constituent particles in the material
body. Similar to classical physics.
He then assumed that the energies of the oscillators were proportional to
an integral multiple n of the frequency .
= nh
Plancks constant: h = 6.626 1034 Js
Photoelectric Effect and Heinrich Hertz
In 1888, Heinrich Hertz discovered that ultraviolet light caused electrons to
be emitted from a metallic surface. This is called the photoelectric effect.

en.wikipedia.org/wiki/File:Photoelectric effect.svg

Photoelectric Effect
Two experimental observations of the photoelectric effect are in stark
contrast with classical wave theory of light.
1. The kinetic energy of the electrons is independent of the intensity of the
incident radiation.
Classical physics predicts that the kinetic energy of the emitted
electrons should be proportional to the intensity of the incident
radiation.
2. There is a threshold frequency 0 characteristic of the metallic surface,
below which no electrons are rejected.
Classical physics predicts that the photoelectric effect should occur
for any frequency of light with sufficient intensity.
4

Photoelectric Effect and Albert Einstein

In order to explain these results, Albert Einstein used Plancks hypothesis,
and extended it in an important way.
Planck applied his quantization concept to the emission and absorption
mechanism of electronic oscillators. Once the light was emitted, it
behaved like a classical wave.
Einstein proposed that the radiation itself existed in small packets of
energy = h, also known as photons.
Einstein showed that the kinetic energy of the ejected electron ( 12 mv2 ) is related
to the incident radiation (h) and the work function of the metal (, similar to
the ionization energy) via
1 2
mv = h
2
1 eV = 1.602 1019 J
Balmer Series for Hydrogen Atoms
Emission spectrum of Hydrogen
410 nm 434 nm

486 nm

656 nm

commons.wikimedia.org/wiki/File:Emission spectrum-H labeled.svg

In 1885, Johann Balmer, apparently through trial and error, deduced a formula
for the wavelengths of these spectral lines.


1
1

= 3.2881 1015 s1
22
n2
where is the frequency of the spectral line, and n is an integer greater than 2.
Empirical Approximations
In trying to find a pattern in the wavelengths or frequencies of the lines
in the atomic hydrogen spectrum, Johann Balmer showed that the plot of the
frequency of some lines versus 1/n2 is a linear plot.


4
14
1 2 Hz
= 8.2202 10
where
n = 3, 4, 5 . . .
n
Johannes Rydberg accounted for all the lines in the hydrogen atomic spectrum
by generalizing the Balmer formula to
!
1
1
= R H
where
R H = 109, 677.57 cm1
2
n21
n2
R H is called the Rydberg constant.
Niels Bohr
In 1913, Niels Bohr explained the line spectra by assuming Plancks idea of
energy being quantized.

en.wikipedia.org/wiki/File:Niels Bohr.jpg

Absorption and Emission

Electronic Transitions
Photon absorption

en.wikipedia.org/wiki/File:AtomicLineAb.png

Photon emission

en.wikipedia.org/wiki/File:AtomicLineSpEm.png

Rotating Systems
Linear and rotating systems (angular)
linear
mass m
speed v = 2rvrot = r
momentum p = mv
KE K = 21 mv2 =
force f = ma

p2
2m

angular
moment of inertia I = mr2
angular speed = 2vrot
angular momentum l = I
rotational KE K = 21 I 2 =
2
inward force f = mvr

l2
2

|L| = |r||p|sin
L

|p
|si
n

L=r

|p|co
s

en.wikipedia.org/wiki/File:Angular momentum definition.svg

Niels Bohr and Angular Momentum

Niels Bohr assumed that the angular momentum of the electron in a
hydrogen atom is quantized.
Classical physics predicts that an electron revolving around a nucleus
will lose energy and spiral into the nucleus, and so a stable orbit of the
electron is classically forbidden.
Bohr first assumed the existence of stationary electron orbitals.
He then specified these orbits by invoking a quantization condition, and
assumed that the angular momentum of the electron must be quantized
l = mvr = nh

where

h =

h
and n = 1, 2 . . .
2

Bohr Radius
Given that the angular force (mv2 /r) is equal to Coulombs law (e2 /4 0 r2 )
mv2
e2
=
2
r
4 0 r
and Bohrs assumption, we get
r=

4 0 h 2 n2
me2

n = 1, 2, . . .

Thus we get the Bohr radius r = 0.529 A(at

n = 1), sometimes denoted by a0 .
Hydrogen Energy Levels
Given that the total energy of the electron is equal to the sum of the kinetic
energy and potential energy
E=

e2
1 2
mv
2
4 0 r

En =

me4 1
820 h2 n2

n = 1, 2, . . .

Given electronic transitions

me4
E = 2 2
8 0 h

1
1
2
2
n1
n2

= h

Setting E = h is called the Bohr frequency condition. The Lyman series

occurs at n = 1, the Balmer series at n = 2, etc.
Rydberg Constant
we can derive the Rydberg constant
By refitting h = hc,
RH =

me4
820 ch3

Using this equation, R H = 109, 737 cm1 , which is 0.5% of the experimental
value of 109, 677.6 cm1
7

122
nm
10
3n
m

Hydrogen Transitions

97

nm

95

656 nm486 nm

n=1
n=2

94

nm

nm

Lyman series

434 nm
410 nm

Balmer series

187

5 nm
128

2n

n=3

10

94

nm

Paschen series

n=4
n=5

n=6

en.wikipedia.org/wiki/File:Hydrogen transitions.svg

3 Wave-Particle Duality of Matter and Energy

Louis de Broglie
In 1924, Louis de Broglie introduced his theory of wave-particle duality
theory of matter, based on the work of Max Planck and Albert Einstein
on light. This theory stated that that any moving particle or object had an
associated wave.

en.wikipedia.org/wiki/File:Broglie Big.jpg

Wave-Particle Duality of Light

Experiments on the properties of light
The dispersion of white light into its spectrum by a prism is an example
of the wavelike property of light.
The photoelectric effect is an example of the shows the particlelike
property of light, that is, behaving as a stream of photons.
Louis de Broglie reasoned that if light can display this wave-particle duality,
then matter might also display wavelike properties under certain conditions.

de Broglie Wavelength
Einstein had shown from relativity theory that the momentum of a photon
is
h
p=

De Broglie argued that both light and matter obey the equation
=

h
h
=
p
mv

This equation predicts that a particle of mass m moving with a velocity v will
have a de Broglie wavelength .
He called the waves associated with material particles matter waves.
This theory was confirmed by electron diffraction experiments.
Electron Diffraction
If the distance between the objects that the waves scatter from is about the
same as the wavelength of the radiation, diffraction occurs and an interference
pattern is observed.
In 1927, C. J. Davisson and L. H. Germer (USA) showed that a beam of
slow electrons is diffracted by a crystal of nickel.
In a similar experiment in that same year, G. P. Thomson of Scotland
directed a beam of electrons at a thin metal foil. He obtained the same
pattern for the diffraction of electrons by aluminum foil as with X-rays of
the same wavelength.
de Broglie Wavelengths of Various Objects
particle
e accelerated
through 100 V

mass (kg)

velocity (m/s)

wavelength (pm)

9.11 1031

5.9 106

120

9.29 1031

5.9 107

12

6.68 1027

1.5 107

6.6 103

1.9 103

3.2 102

1.1 1021

golf ball

0.045

30

4.9 1022

baseball

0.140

25

1.9 1022

e accelerated
through 10,000 V
particle
from radium
22-caliber bullet

4 Quantum Mechanical Model of the Atom

Standing Wave
De Broglie suggested that the electron traveling periodically in a circular
path around the nucleus in a hydrogen atom could be thought of as a standing
wave with a characteristic wavelength.
A standing wave (also known as a stationary wave) is a wave that remains in
a constant position.

n= 3

3<n<4

n=4

en.wikipedia.org/wiki/File:Harmonic partials on strings.svg

The Quantum Condition (1)

As the electron revolves around the proton, it has a wavelength
associated with it.
For the orbit to be stable, it is reasonable to assume that the wave must
match, or be in phase, as the electron makes one complete revolution.
Otherwise, there will be cancellation of amplitude upon each revolution,
and the wave will disappear.
The Quantum Condition (2)
Thus an integral number of complete wavelengths must fit around the
circumference of the orbit. Thus we have the quantum condition
2r = n

n = 1, 2, 3 . . .

If we substitute de Broglies relation, we obtain the Bohr quantization

condition
mvr = nh
Velocity of an Electron
Using this equation we can calculate the velocity of an electron in the first
Bohr orbit
v

nh
mr

1.055 1034 Js
(9.11 1031 kg)(5.29 1011 m)

= 2.91 106 m/s

Almost 1% of the speed of light.
10

Werner Heisenberg
In 1927, Werner Heisenberg published the theory called the Uncertainty
Principle which was a key development to understanding the physical
behavior of particles such as the electrons.

en.wikipedia.org/wiki/File:Bundesarchiv Bild183-R57262, Werner Heisenberg.jpg

Measurement of Electron Position

Consider a measurement of the position of an electron.
To locate an electron within a distance x, we must use a measuring
device that has a spatial resolution less than x. Use light with
wavelength x. For a more accurate measurement, use a smaller
wavelength.
The photon has momentum p = h/. During the interaction with the
electron, the photon will transfer its momentum to the electron.
Smaller leads to higher p, thus increasing the momentum change of the
electron.
Heisenberg Uncertainty Principle
Werner Heisenberg showed that it is not possible to determine exactly how
much momentum is transferred to the electron.
If we wish to locate any particle to within a distance x, then we
automatically introduce an uncertainty in the momentum of the particle.
Heisenbergs Uncertainty Principle
xp

h
4

This uncertainty is not due to poor measurement or poor experimental

technique, but is a fundamental property of the act of measurement itself.
Significance in Objects
Using Heisenbergs uncertainty principle,
A 0.14 kg baseball travelling at 90 mph has a momentum of 5.6 kg/(m-s).
Given an uncertainty of a millionth of 1.0 %, p = 5.6 108 kg/(m-s).
This gives an uncertainty in distance of x = 1.2 1026 m, which is a
completely inconsequential distance.
If we wish to locate an electron within an atom with an uncertainty of
x = 50 pm, the uncertainty in momentum is p = 1.3 1023 kg/(m-s).
Since p = mv, then the uncertainty in speed is v = 1.4 107 m/s, which
is a very large uncertainty in speed.
This principle is of no consequence for macroscopic bodies. But it has very
important consequences in dealing with atomic and subatomic particles.
11

Erwin Schrodinger

In 1926, Erwin Schrodinger

was formulated the Schrodinger

Equation,
which that describes how the quantum state of a physical system changes in
time.

The time-dependent Schrodinger

Equation

ih

= H
t

The time-independent Schrodinger

Equation
= E
H

en.wikipedia.org/wiki/File:Erwin Schrodinger.jpg

Max Born

Max Born proposed instead that Schrodingers

wave function described
not the electron but rather all its possible states, and thus could be used to
calculate the probability of finding an electron at any given location around
the nucleus.
probability density = 2

en.wikipedia.org/wiki/File:Max Born.jpg

Quantum Mechanics

The Schrodinger
Equation (SE)

ih

= H
t

and

= E
H

The SE incorporates both wavelike and particle-like behavior of the

electron. This branch study is called quantum mechanics.
12

 Wave functions, designated by the symbol , describe the motion of the

particles. The square of the wave function, 2 , provides information
about the electron?s location when it is in an allowed energy state.
Due to the uncertainty principle, we speak of the probability that the
electron will be in a certain region of space at a given instant. 2 is called
the probability density.
Hydrogen Atom Wave Functions

Solutions of the Schrodinger

equation for the hydrogen atom give the wave
functions () for the electron in the hydrogen atom. These wave functions are
called orbitals.
These functions are often written in the spherical polar coordinate
system.
m
nlml (r, , ) = Rnl (r )Yl l (, )
(r, , ) = R(r )Y (, )
The function Rnl (r ) is called the radial wave function
m

The function Yl l (, ) is called the angular wave function.

Each orbital has three quantum numbers to define it, each corresponding
to a dimension in a 3D system.
Polar Coordinate System

r
r cos

r cos s
in

r sin sin

commons.wikimedia.org/wiki/File:Polar-coordinates-3D.svg

r2
x

= x 2 + y2 + z2
= r sin cos
y = r sin sin
z = r cos

5 Quantum Numbers and Atomic Orbitals

5.1

The Four Quantum Numbers

First QN: Principal Quantum Number

The first quantum is number n is the principal quantum number.
describes the electron shell, or energy level

13

 The value of n ranges from 1 to n (1, 2, . . . n), where n is the shell

containing the outermost electron of that atom.
For example, in cesium (Cs), the outermost valence electron is in the
shell with energy level 6, so an electron in cesium can have n values
from 1 to 6.
The energy levels with higher n values are those farther away from the
nucleus, have higher energies, and are more easily taken away from their
orbits.
Second QN: Azimuthal Quantum Number
The second quantum number l is the azimuthal quantum number.
describes the subshell
physical significance: l determines the angular distribution or shape of
the orbital
The value of l are 0, 1 . . . (n 1).
l
0
1
2
3
4

Subshell label
s
p
d
f
g

Max electrons
2
6
10
14
18

Historical name
sharp
principal
diffuse
fundamental
(next in alphabet after f )

Third QN: Magnetic Quantum Number

The third quantum number ml is the magnetic quantum number
describes the specific orbital (or cloud) within that subshell
physical significance: ml determines the orientation of the orbital
these are degenerate orbitals, or orbitals with the same energy, as
indicated by ml
values of ml are l, l + 1 . . . 0 . . . l 1, l.
For example, the s subshell (l = 0) contains only one orbital, and
therefore the ml of an electron in an s subshell will always be 0.
The p subshell (l = 1) contains three orbitals, so the ml of an electron
in a p subshell will be -1, 0, or 1.
The d subshell (l = 2) contains five orbitals, with ml values of -2, -1,
0, 1, and 2.
The First Few Radial Wave Functions
The first few radial wave functions Rnl (r ), where Z is the nuclear charge,

14

a0 is the Bohr radius, and = Zr/a0 .

1s

R10 (r ) = 2

2s

R20 (r ) =

2p

R21 (r ) =

3s

R30 (r ) =

3p

R31 (r ) =

3d

R32 (r ) =

Z
a0

3/2


Z 3/2
(2 )e/2
2a0


Z 3/2 /2
1

e
3 2a0


Z 3/2
2
(27 18 + 22 )e/3
27 3a0


2Z 3/2
1
(6 )e/3
27 3a0


Z 3/2 2 /3
4

e
27 10 3a0

Some Spherical Harmonics Yl l (, )

m
The first few spherical harmonics Yl l (, )

5.2

1
(4 )1/2
 1/2
3
cos
4
 1/2
3

sin ei
8
 1/2
3
sin ei
8


5 1/2
(3 cos2 1)
16

Y00

Y10

Y11

Y11

Y20

Y21

Y21

Y22

Y22


15 1/2
sin cos ei
8
 1/2
15
sin cos ei
8


15 1/2
sin2 e2i
32


15 1/2
sin2 e2i
32


Atomic Orbitals

The 1s Orbital
The complete wave function for the 1s hydrogen orbital is
 3/2
1
er/a0
Z
0
q
e
=
1s (r, , ) = R10 (r ) Y0 (, ) = 2
a0
(4 )1/2
a30

The probability density of finding a electron at a distance r from the nucleus is

 
1 1 3 r/a0
2
e
1s (r, , ) =
a0
15

The s Orbital

www.chem1.com/acad/webtext/atoms/atpt-images/s-orb shells.png

The p Orbitals

p x orbital

py orbital

pz orbital
en.wikipedia.org/wiki/Atomic orbitals

16

The d Orbitals

d xy orbital

d xz orbital

dyz orbital

d x2 y2 orbital

dz2 orbital

en.wikipedia.org/wiki/Atomic orbitals

Fourth QN: Spin Quantum Number

The fourth quantum number is the spin quantum number
symbol: ms
describes the spin of the electron within that orbital
an electron can have ms
counterclockwise

17

1
2

clockwise, or ms

21

5.3

Multielectron Atoms

Electronic Repulsion

Schrodinger
developed his wave equation for the hydrogen atom which
contains just one electron. For multielectron atoms, a new factor arises: mutual
repulsion between electrons.
Due to this repulsion between them, the electrons tend to stay away from
one another, and their motions become inextricably entangled.
To solve this many-particle problem, an approximation is to consider the
electrons, one by one, in the environment established by the nucleus and
the other electrons.
When this is done, the electron orbitals obtained are of the same types
as those obtained for the hydrogen atom; they are called hydrogen-like
orbitals.
Compared with the hydrogen atom, the angular parts of the orbitals of a
multielectron atom are unchanged, but the radial parts are different.
Penetration and Shielding
Factors that affect the effective nuclear charge:
Electrons in orbitals closer to the nucleus screen or shield the nucleus
from electrons farther away. In effect, the screening electrons reduce
the effectiveness of the nucleus in attracting the particular more-distant
electron. They effectively reduce the nuclear charge.
The s orbital, which has a probability at the nucleus, can be closer to
the nucleusmore penetrating than the p or d orbitals, which have zero
probability at the nucleus.This ability is called penetration.
Effective Nuclear Charge
The nuclear charge that an electron would experience if there were no
intervening electrons is Z, the atomic number. The nuclear charge that an
electron actually experiences is reduced by intervening electrons to a value
of Zeff , called the effective nuclear charge.
Orbital Energy Levels
To summarize:
Compared with a p electron in the same principal shell, an s electron is
more penetrating, not as well screened, experiences a higher Zeff , and is
held more tightly, and is at a lower energy than a p electron.
The same is true between the p and the z electrons.
Thus, the energy level of a principal shell is split into separate levels for
its subshells.
There is no further splitting of energies within a subshell, however, which
experience the same Zeff .

5.4

Electron Configurations

Rules for Electron Assignment

The electron configuration of an atom is a designation of how electrons are
distributed among various orbitals in principal shells and subshells. The rules
for this distribution are:
Electrons occupy orbitals in a way that minimizes the energy of the atom.
18

 The Pauli exclusion principle. No two electrons in an atom can have all
four quantum numbers alike.
Hunds rule. When orbitals of identical energy (degenerate orbitals) are
available, electrons initially occupy these orbitals singly.
Pauli Exclusion Principle
The Pauli Exclusion Principle states that no two electrons can have the
same set of four quantum numbers (n, l, ml , ms ). An orbital can hold a
maximum of two electrons, and they must have opposite spins.
Aufbau Principle
The Aufbau Principle electrons fill orbitals starting at the lowest available
(possible) energy states before filling higher states (e.g. 1s before 2s).
Also called the Building-Up Principle
The order in which these orbitals are filled is given by the (n + l ) rule, which
states that given two orbitals, the one which has a higher n value but a lower
(n + l ) value is considered to be of a lower energy level.
Also called the Madelung rule or the Klechkowski rule.
3d is higher energy than 4s since the (n + l ) of 3d is 5 while the (n + l ) of
4s is 4.
Klechkovski Rule

en.wikipedia.org/wiki/File:Klechkovski rule.svg

Hunds Rule
Hunds Rule states that for degenerate orbitals, the lowest energy is
attained when the number of electrons with the same spin is maximized.
also called Hunds Rule of Maximum Multiplicity.
Since electrons repel each other, the electrons attain the lowest energy
level by staying as far apart from each other by staying in different
sub-orbitals.

19

Summary
Hydrogen atom
4s

A typical multielectron atom

. . . (4p, 4d, 4f)

4p

3s

3p

3d

3d
4s
3p

2s

2p

Energy

Energy

3s

1s

2p
2s

1s

Summary: Hunds Rule

correct

a.
1s

2s

2p
correct

b.
1s

2s

2p

c.

(since this is the 1 electron in the p sublevel

it can be either "spin-up" or "spin-down")

incorrect

1s

2s

2p

(the spin of the 2nd electron depends on the spin of the

1st electron, even though they aren't in the same orbital)

correct

d.
1s

2s

2p

(as long as you draw the first electron in each orbital as

"spin-up", you will draw a correct orbital diagram)

commons.wikimedia.org/wiki/File:Hund%27s Rule.svg

Examples
Symbol
Li
Be
B
C
N
O
F
Ne
Ge
Au

# e
3
4
5
6
7
8
9
10
32
79

Electron configuration
1s2 2s1
1s2 2s2
1s2 2s2 2p1
1s2 2s2 2p2
1s2 2s2 2p3
1s2 2s2 2p4
1s2 2s2 2p5
1s2 2s2 2p6
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4 f 14 5d9

20