Chapter 2

Atomic Structure
Importance of the
Hydrogen Atom
The hydrogen atom is the only
atomic system that can be solved
exactly
Much of what was learned in the
twentieth century about the
hydrogen atom, with its single
electron, can be extended to such
single-electron ions as He+ and
More Reasons the Hydrogen
Atom is Important
The hydrogen atom is an ideal
system for performing precision
tests of theory against
experiment
Also for improving our understanding of atomic structure

The quantum numbers that are

used to characterize the allowed
states of hydrogen can also be
used to investigate more complex
atoms
Final Reasons for the Importance
of the Hydrogen Atom

The basic ideas about atomic

structure must be well
understood before we attempt to
deal with the complexities of
molecular structures and the
electronic structure of solids
The full mathematical solution of
the Schrödinger equation applied
Atomic Spectra
A discrete line spectrum is
observed when a low-pressure
gas is subjected to an electric
discharge
Observation and analysis of these
spectral lines is called emission
spectroscopy
The simplest line spectrum is that
Emission Spectra Examples
Uniqueness of Atomic Spectra
Other atoms exhibit completely
different line spectra
Because no two elements have
the same line spectrum, the
phenomena represents a practical
and sensitive technique for
identifying the elements present
in unknown samples
Absorption Spectroscopy
An absorption spectrum is
obtained by passing white light
from a continuous source
through a gas or a dilute solution
of the element being analyzed
The absorption spectrum
consists of a series of dark lines
superimposed on the continuous
Absorption Spectrum,
Example

A practical example is the continuous spectrum

emitted by the sun
The radiation must pass through the cooler gases
of the solar atmosphere and through the Earth’s
atmosphere
Balmer Series
In 1885, Johann Balmer
found an empirical
equation that correctly
predicted the four
visible emission lines of
hydrogen
Hα is red, λ = 656.3 nm
Hβ is green, λ = 486.1 nm
Hγ is blue, λ = 434.1 nm
Hδ is violet, λ = 410.2 nm
Emission Spectrum of
Hydrogen – Equation
The wavelengths of hydrogen’s
spectral lines can be found from
1  1 1 
 RH  2
 2 
λ  2 n 

RH is the Rydberg constant

RH = 1.097 373 2 x 107 m-1
n is an integer, n = 3, 4, 5,…
The spectral lines correspond to different values of n
Other Hydrogen Series
Other series were also discovered
and their wavelengths
1  1  can be
 R  1   n  2 , 3 , 4 ,
calculated
H 2
λ  n 

Lyman series: 1  R  1  1  n  4, 5, 6,

H  2 
λ 3 n2 

Paschen series:
1
R
 1 1
H 2  2  n  5 , 6 , 7 ,
λ 4 n 

Brackett series:
Joseph John Thomson
1856 – 1940
English physicist
Received Nobel Prize in 1906
Usually considered the
discoverer of the electron
Worked with the deflection
of cathode rays in an electric
field
Opened up the field of subatomic
particles
Early Models of the Atom,
Thomson’s
J. J. Thomson established
the charge to mass ratio for
electrons
His model of the atom
A volume of positive charge
Electrons embedded throughout
the volume
Rutherford’s Thin Foil
Experiment
Experiments done in 1911
A beam of positively
charged alpha particles hit
and are scattered from a
thin foil target
Large deflections could not
be explained by Thomson’s
model
Early Models of the Atom,
Rutherford’s
Rutherford
Planetary model
Based on results of thin foil
experiments
Positive charge is
concentrated in the center of
the atom, called the nucleus
Electrons orbit the nucleus like
planets orbit the sun
Difficulties with the
Rutherford Model
Atoms emit certain discrete characteristic
frequencies of electromagnetic radiation
The Rutherford model is unable to explain this phenomena
Rutherford’s electrons are undergoing a
centripetal acceleration
It should radiate electromagnetic waves of the same frequency
The radius should steadily decrease as this radiation is given off
The electron should eventually spiral into the nucleus
It doesn’t
Niels Bohr
1885 – 1962
Danish physicist
An active participant in the
early development of
quantum mechanics
Headed the Institute for
Advanced Studies in
Copenhagen
Awarded the 1922 Nobel
Prize in physics
For structure of atoms and the
radiation emanating from them
The Bohr Theory of Hydrogen
In 1913 Bohr provided an
explanation of atomic spectra that
includes some features of the
currently accepted theory
His model includes both classical
and non-classical ideas
He applied Planck’s ideas of
quantized energy levels to
Bohr’s Theory, cont.
This model is now considered
obsolete
It has been replaced by a
probabilistic quantum-mechanical
theory
The model can still be used to
develop ideas of energy
quantization and angular
Bohr’s Assumptions for
Hydrogen, 1
The electron moves in
circular orbits around
the proton under the
electric force of
attraction
The Coulomb force produces
the centripetal acceleration
Bohr’s Assumptions, 2
Only certain electron orbits are
stable
These are the orbits in which the atom does not emit energy in the form of
electromagnetic radiation
Therefore, the energy of the atom remains constant and classical mechanics
can be used to describe the electron’s motion
This representation claims the centripetally accelerated electron does not emit
energy and therefore does not eventually spiral into the nucleus
Bohr’s Assumptions, 3
Radiation is emitted by the atom when the electron
makes a transition from a more energetic initial
state to a lower-energy orbit
The transition cannot be treated classically
The frequency emitted in the transition is related to the change in
the atom’s energy
The frequency is independent of frequency of the electron’s
orbital motion
The frequency of the emitted radiation is given by
Ei – Ef = hƒ
If a photon is absorbed, the electron moves to a higher energy level
Bohr’s Assumptions, 4
The size of the allowed electron
orbits is determined by a
condition imposed on the
electron’s orbital angular
momentum
The allowed orbits are those for
which the electron’s orbital
angular momentum about the
Mathematics of Bohr’s
Assumptions and Results
Electron’s orbital angular momentum
mevr = nħ where n = 1, 2, 3,…
The total energy of the atom is
2
1 e
E  K  U  mev 2  ke
2 r
The total energy can also be expressed as
kee 2
E
2r is negative, indicating a bound electron-
Note, the total energy
proton system
Bohr Radius
The radii 2of2 the Bohr orbits are
n
quantized
rn 
mke 2
n  1, 2, 3 ,
e e

This shows that the radii of the allowed orbits have discrete values—they are
quantized
When n = 1, the orbit has the smallest radius, called the Bohr radius, ao
ao = 0.052 9 nm
Radii and Energy of Orbits
A general expression
for the radius of any
orbit in a hydrogen
atom is
rn = n2ao
The energy of any orbit
is
k ee 2  1 
En    2  n  1, 2,3, 
2ao  n 
This becomes
En = - 13.606 eV / n2
Specific Energy Levels
Only energies satisfying the
previous equation are allowed
The lowest energy state is called
the ground state
This corresponds to n = 1 with E = –13.606 eV

The ionization energy is the

energy needed to completely
remove the electron from the
ground state in the atom
Energy Level Diagram
Quantum numbers are
given on the left and
energies on the right
The uppermost level,
E = 0, represents the
state for which the
electron is removed
from the atom
Adding more energy than this
amount ionizes the atom
Active Figures 42.7 and 42.8
Use the active figure to
choose initial and final
energy levels
Observe the transition
in both figures

PLAY
ACTIVE FIGURE
Frequency of Emitted Photons
The frequency of the photon
emitted when the electron makes
a transition
Ei  Ef kefrom
e 2  1 an1 outer orbit to
ƒ   2  2
an inner h orbit
2ao h is
nf ni 

It is convenient to look at the

wavelength instead
Wavelength of Emitted
Photons
The wavelengths are found by
1 ƒ k ee 2  1 1  1 1
   2  2   RH  2  2 
λ c 2aohc  nf ni   nf ni 

The value of RH from Bohr’s

analysis is in excellent agreement
with the experimental value
Extension to Other Atoms
Bohr extended his model for
hydrogen to other elements in
which all a but one electron had
r  n  2 o
been removed
n
Z
k ee 2  Z 2 
En    2  n  1, 2, 3 ,
2ao  n 

Z is the atomic number of the element and is the number of protons in the
nucleus
Difficulties with the Bohr
Model
Improved spectroscopic
techniques found that many of
the spectral lines of hydrogen
were not single lines
Each “line” was actually a group of lines spaced very close together

Certain single spectral lines split

into three closely spaced lines
when the atoms were placed in a
magnetic field
Bohr’s Correspondence
Principle
Bohr’s correspondence principle
states that quantum physics
agrees with classical physics
when the differences between
quantized levels become
vanishingly small
Similar to having Newtonian mechanics be a special case of relativistic
mechanics when v << c
The Quantum Model of the
Hydrogen Atom
The potential energy function for
the hydrogen
2
atom is
e
U (r )   k e
r

ke is the Coulomb constant

r is the radial distance from the proton to the electron
The proton is situated at r = 0
Quantum Model, cont.
The formal procedure to solve the
hydrogen atom is to substitute
U(r) into the Schrödinger
equation, find the appropriate
solutions to the equations, and
apply boundary conditions
Because it is a three-dimensional
problem, it is easier to solve if the
Quantum Model, final
ψ(x, y, z) is converted to ψ(r,
θ, φ)
Then, the space variables
can be separated:
ψ(r, θ, φ) = R(r), ƒ(θ), g(φ)
When the full set of
boundary conditions are
applied, we are led to three
different quantum numbers
for each allowed state
Quantum Numbers, General
The three different quantum
numbers are restricted to integer
values
They correspond to three degrees
of freedom
Three space dimensions
Principal Quantum Number
The first quantum number is
associated with the radial
function R(r)
It is called the principal quantum number
It is symbolized by n

The potential energy function

depends only on the radial
coordinate r
The energies of the allowed
Orbital and Orbital Magnetic
Quantum Numbers
The orbital quantum number is
symbolized by ℓ
It is associated with the orbital angular momentum of the electron
It is an integer

The orbital magnetic quantum

number is symbolized by mℓ
It is also associated with the angular orbital momentum of the electron and is
an integer
Quantum Numbers, Summary
of Allowed Values
The values of n can range from 1 to ¥
The values of ℓ can range from 0 to n - 1
The values of mℓ can range from –ℓ to ℓ
Example:
If n = 1, then only ℓ = 0 and mℓ = 0 are permitted
If n = 2, then ℓ = 0 or 1
If ℓ = 0 then mℓ = 0
If ℓ = 1 then mℓ may be –1, 0, or 1
Quantum Numbers,
Summary Table
Shells
Historically, all states having the
same principle quantum number
are said to form a shell
Shells are identified by letters K, L, M,…

All states having the same values

of n and ℓ are said to form a
subshell
The letters s, p, d, f, g, h, .. are used to designate the subshells for which ℓ = 0,
1, 2, 3,…
Shell and Subshell Notation,
Summary Table
Wave Functions for Hydrogen
The simplest wave function for
hydrogen is the one that
describes1 ther a1s state and is
ψ1s (r )  o
e
designated πao3 ψ1s(r)

As ψ1s(r) approaches zero, r

approaches ¥ and is normalized
Probability Density
The probability density for the 1s
state is
2  1  2r a
ψ1s   3  e o

 πao 

The radial probability density

function P(r) is the probability per
unit radial length of finding the
electron in a spherical shell of
Radial Probability Density
A spherical shell of
radius r and thickness
dr has a volume of 4πr2
dr
The radial probability
function is
P(r) = 4πr2 |ψ|2
P(r) for 1s State of Hydrogen
The radial probability
density function for the
hydrogen atom in its
ground state is
 4r 2  2r ao
P1s (r )   3  e
 ao 
The peak indicates the
most probable location
The peak occurs at the
Bohr radius
P(r) for 1s State of Hydrogen,
cont.
The average value of r for the
ground state of hydrogen is 3/2
ao
The graph shows asymmetry, with much more area to the right of the peak

According to quantum
mechanics, the atom has no
sharply defined boundary as
suggested by the Bohr theory
Electron Clouds
The charge of the electron is
extended throughout a
diffuse region of space,
commonly called an electron
cloud
This shows the probability
density as a function of
position in the xy plane
The darkest area, r = ao,
corresponds to the most
probable region
Wave Function of the 2s state
The next-simplest wave function
for the hydrogen atom is for the
2s state
n = 2; ℓ = 0

The normalized
1 wave
1  function
r  is 3
2
r
ψ2s (r )     2   e 2 ao

4 2π  ao   ao 

ψ2s depends only on r and is spherically symmetric

Comparison of 1s and 2s
States
The plot of the radial
probability density for
the 2s state has two
peaks
The highest value of P
corresponds to the
most probable value
In this case, r » 5ao
Active Figure 42.12
Use the active figure to
choose values of r/ao
Find the probability that
the electron is located
between two values

PLAY
ACTIVE FIGURE
Physical Interpretation of ℓ
The magnitude of the angular
momentum of an electron moving
in a circle of radius
 r is
L
L = mevr
The direction of is
perpendicular to the plane of the
circle
The direction is given by the right hand rule

In the Bohr model, the angular

Physical Interpretation
of ℓ, cont.
According to quantum
mechanics, an atom in a state
whose principle quantum number
is n can take on the following
discrete
1
λ
 Rvalues
 1

2
 of
 the magnitude
1 
n 
H 2 2

of the orbital angular momentum:

L can equal zero, which causes great difficulty when attempting to apply
classical mechanics to this system
Physical Interpretation of mℓ
The atom possesses an orbital
angular momentum
There is a sense of rotation of the
electron around the nucleus, so
that a magnetic moment is
present due to this μ
angular

momentum 
B
There are distinct directions
Physical Interpretation of mℓ, 2

Because the magnetic momentμ

of the atom

L
can be related to the
μ

angular momentum vector, L , the
discrete direction of translates

into the fact that the direction
L of
is quantized
Therefore, Lz, the projection of
along the z axis, can have only
Physical Interpretation of mℓ, 3
The orbital magnetic quantum
number mℓ specifies the allowed
values of the z component of
orbital

angular momentum
Lz =L mℓ
The quantization of the possible
orientations of with respect to
an external magnetic field is often
Physical Interpretation of mℓ, 4

Ldoesnot point in a specific
direction
Even though its z-component is fixed
Knowing all the components is inconsistent with the uncertainty principle

Imagine that
must lie anywhere
L
on the surface of a cone that
makes an angle θ with the z axis
Physical Interpretation of mℓ,
final
θ is also quantized
Its values are specified
through
Lz m
cos θ  
L    1
mℓ is never greater than
ℓ, therefore θ can never
be zero
Zeeman Effect
The Zeeman effect is the
splitting of spectral lines in a
strong magnetic field
In this case the upper level,
with ℓ = 1, splits into three
different levels
corresponding to the three
different directions of µ
Spin Quantum Number ms
Electron spin does not come from
the Schrödinger equation
Additional quantum states can be
explained by requiring a fourth
quantum number for each state
This fourth quantum number is
the spin magnetic quantum
number ms
Electron Spins
Only two directions exist for
electron spins
The electron can have spin
up (a) or spin down (b)
In the presence of a
magnetic field, the energy of
the electron is slightly
different for the two spin
directions and this produces
doublets in spectra of
certain gases
Electron Spins, cont.
The concept of a spinning electron is conceptually
useful
The electron is a point particle, without any spatial
extent
Therefore the electron cannot be considered to be actually
spinning
The experimental evidence supports the electron
having some intrinsic angular momentum that can
be described by ms
Dirac showed this results from the relativistic
properties of the electron
Spin Angular Momentum
The total angular momentum of a
 
particular Lelectron state contains
S
both an orbital contribution and
a spin contribution
Electron spin can be described by
a single quantum number s,
whose value can only be s = ½
The spin angular momentum of
Spin Angular Momentum, cont
The magnitude of the spin
angular momentum is
3
S s(s  1)  
2

The spin angular momentum can

have two orientations relative to a
z axis, specified by the spin
quantum number ms = ± ½
ms = + ½ corresponds to the spin up case
Spin Angular Momentum, final
The z component of
spin angular momentum
is Sz = msh = ± ½ h
Spin angular moment is
quantized
Spin Magnetic Moment
The spin magnetic moment µspin
is related to the spin angular
 e
momentum
μspin   Sby
me

The z component e of the spin

magnetic 
μspin , z moment can have
2me
values
Quantum States
There are eight quantum states
corresponding to n = 2
These states depend on the addition of the possible values of ms
Table 42.3 summarizes these states
Quantum Numbers for n = 2 State
of Hydrogen
Wolfgang Pauli
1900 – 1958
Austrian physicist
Important review article on
relativity
At age 21
Discovery of the exclusion
principle
Explanation of the
connection between
particle spin and statistics
Relativistic quantum
electrodynamics
Neutrino hypothesis
Hypotheses of nuclear spin
The Exclusion Principle
The four quantum numbers discussed so far can
be used to describe all the electronic states of an
atom regardless of the number of electrons in its
structure
The exclusion principle states that no two
electrons can ever be in the same quantum state
Therefore, no two electrons in the same atom can have the
same set of quantum numbers
If the exclusion principle was not valid, an atom
could radiate energy until every electron was in
the lowest possible energy state and the chemical
nature of the elements would be modified
Filling Subshells
The electronic structure of
complex atoms can be viewed as
a succession of filled levels
increasing in energy
Once a subshell is filled, the next
electron goes into the lowest-
energy vacant state
If the atom were not in the lowest-energy state available to it, it would radiate
energy until it reached this state
Orbitals
An orbital is defined as the atomic state
characterized by the quantum numbers n, ℓ and
mℓ
From the exclusion principle, it can be seen that
only two electrons can be present in any orbital
One electron will have spin up and one spin down
Each orbital is limited to two electrons, the number
of electrons that can occupy the various shells is
also limited
Allowed Quantum States,
Example with n = 3

In general, each shell can accommodate up to

2n2 electrons
Hund’s Rule
Hund’s Rule states that when an
atom has orbitals of equal energy,
the order in which they are filled
by electrons is such that a
maximum number of electrons
have unpaired spins
Some exceptions to the rule occur in elements having subshells that are close
to being filled or half-filled
Configuration of Some
Electron States
Periodic Table
Dmitri Mendeleev made an early
attempt at finding some order
among the chemical elements
He arranged the elements
according to their atomic masses
and chemical similarities
The first table contained many
blank spaces and he stated that
Periodic Table, cont.
By noting the columns in which
some missing elements should
be located, he was able to make
rough predictions about their
chemical properties
Within 20 years of the
predictions, most of the elements
were discovered
Periodic Table, Explained
The chemical behavior of an
element depends on the
outermost shell that contains
electrons
For example, the inert gases (last
column) have filled subshells and
a wide energy gap occurs
between the filled shell and the
Hydrogen Energy Level
Diagram Revisited
The allowed values of ℓ are
separated horizontally
Transitions in which ℓ does
not change are very unlikely
to occur and are called
forbidden transitions
Such transitions actually can
occur, but their probability is very
low compared to allowed
transitions
Selection Rules
The selection rules for allowed transitions are
Δℓ = ±1
Δmℓ = 0, ±1
The angular momentum of the atom-photon
system must be conserved
Therefore, the photon involved in the process
must carry angular momentum
The photon has angular momentum equivalent to that of a
particle with spin 1
A photon has energy, linear momentum and angular momentum
Multielectron Atoms
For multielectron atoms, the
positive nuclear charge Ze is
largely shielded by the negative
charge of the inner shell
electrons
The outer electrons interact with
2 a net charge that is smaller than the nuclear
charge 13 .6 Z
E 
n
eff
eV
Allowed energies are n2

Zeff depends on n and ℓ

X-Ray Spectra
These x-rays are a result of
the slowing down of high
energy electrons as they
strike a metal target
The kinetic energy lost can
be anywhere from 0 to all of
the kinetic energy of the
electron
The continuous spectrum is
called bremsstrahlung, the
German word for “braking
radiation”
X-Ray Spectra, cont.
The discrete lines are called
characteristic x-rays
These are created when
A bombarding electron collides with a target atom
The electron removes an inner-shell electron from orbit
An electron from a higher orbit drops down to fill the vacancy
X-Ray Spectra, final
The photon emitted during this
transition has an energy equal to
the energy difference between the
levels
Typically, the energy is greater
than 1000 eV
The emitted photons have
wavelengths in the range of 0.01
Moseley Plot
Henry G. J. Moseley plotted
the values of atoms as shown
λ is the wavelength of the Kα
line of each element
The Kα line refers to the photon
emitted when an electron falls from
the L to the K shell
From this plot, Moseley
developed a periodic table in
agreement with the one based
on chemical properties
Stimulated Absorption

When a photon has energy hƒ equal to the

difference in energy levels, it can be absorbed by
the atom
This is called stimulated absorption because the
photon stimulates the atom to make the upward
transition
Active Figure 42.25
Use the active figure to
adjust the energy
difference between the
states
Observe stimulated
absorption

PLAY
ACTIVE FIGURE
Spontaneous Emission
Once an atom is in an
excited state, the
excited atom can make
a transition to a lower
energy level
Because this process
happens naturally, it is
known as spontaneous
emission
Stimulated Emission
In addition to
spontaneous emission,
stimulated emission
occurs
Stimulated emission
may occur when the
excited state is a
metastable state
Stimulated Emission, cont.
A metastable state is a state whose lifetime is
much longer than the typical 10-8 s
An incident photon can cause the atom to return to
the ground state without being absorbed
Therefore, you have two photons with identical
energy, the emitted photon and the incident
photon
They both are in phase and travel in the same direction
Active Figure 42.27
Use the active figure to
adjust the energy
difference between
states
Observe the stimulated
emission

PLAY
ACTIVE FIGURE
Lasers – Properties of
Laser Light
Laser light is coherent
The individual rays in a laser beam maintain a fixed phase relationship with
each other

Laser light is monochromatic

The light has a very narrow range of wavelengths

Laser light has a small angle of

divergence
The beam spreads out very little, even over long distances
Lasers – Operation
It is equally probable that an
incident photon would cause
atomic transitions upward or
downward
Stimulated absorption or stimulated emission

If a situation can be caused where

there are more electrons in
excited states than in the ground
state, a net emission of photons
Lasers – Operation, cont.
The photons can stimulate other
atoms to emit photons in a chain
of similar processes
The many photons produced in
this manner are the source of the
intense, coherent light in a laser
Conditions for Build-Up of
Photons
The system must be in a state of population
inversion
The excited state of the system must be a
metastable state
In this case, the population inversion can be established and
stimulated emission is likely to occur before spontaneous
emission
The emitted photons must be confined in the
system long enough to enable them to stimulate
further emission
This is achieved by using reflecting mirrors
Laser Design – Schematic

The tube contains the atoms that are the active medium
An external source of energy pumps the atoms to excited
states
The mirrors confine the photons to the tube
Mirror 2 is only partially reflective
Energy-Level Diagram for
Neon in a Helium-Neon Laser
The atoms emit 632.8-
nm photons through
stimulated emission
The transition is E3* to
E2
* indicates a metastable state
Laser Applications
Applications include:
Medical and surgical procedures
Precision surveying and length measurements
Precision cutting of metals and other materials
Telephone communications