Chapter 28

Atomic Physics
Importance of Hydrogen
Atom
 Hydrogen is the simplest atom
 The quantum numbers used to
characterize the allowed states of
hydrogen can also be used to
describe (approximately) the
allowed states of more complex
atoms
 This enables us to understand the
periodic table
More Reasons the Hydrogen
Atom is so Important
 The hydrogen atom is an ideal system
for performing precise comparisons of
theory with experiment
 Also for improving our understanding of
atomic structure
 Much of what we know about the
hydrogen atom can be extended to
other single-electron ions
 For example, He+ and Li2+
 Sir Joseph John Thomson
 “J. J.” Thomson
 1856 - 1940
 Discovered the
electron
 Did extensive work
with cathode ray
deflections
 1906 Nobel Prize for
discovery of electron
Early Models of the Atom
 J.J. Thomson’s
model of the atom
 A volume of positive
charge
 Electrons embedded
throughout the
volume
 A change from
Newton’s model of
the atom as a tiny,
hard, indestructible
sphere
Early Models of the Atom,
2
 Rutherford, 1911
 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
 Scattering Experiments

 The source was a naturally radioactive material

that produced alpha particles
 Most of the alpha particles passed though the foil
 A few deflected from their original paths
 Some even reversed their direction of travel
 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 and so 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,
but it doesn’t
 Emission Spectra
 A gas at low pressure has a voltage
applied to it
 A gas emits light characteristic of the gas
 When the emitted light is analyzed with a
spectrometer, a series of discrete bright
lines is observed
 Each line has a different wavelength and color
 This series of lines is called an emission
spectrum
Examples of Emission
Spectra
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 = 1, 2, 3, …
 The spectral lines correspond to different
values of n
 Spectral Lines of Hydrogen
 The Balmer Series
has lines whose
wavelengths are
given by the
preceding equation
 Examples of spectral
lines
 n = 3,  = 656.3 nm
 n = 4,  = 486.1 nm
Absorption Spectra
 An element can also absorb light at specific
wavelengths
 An absorption spectrum can be obtained by
passing a continuous radiation spectrum
through a vapor of the gas
 The absorption spectrum consists of a
series of dark lines superimposed on the
otherwise continuous spectrum
 The dark lines of the absorption spectrum
coincide with the bright lines of the emission
spectrum
Applications of Absorption
Spectrum
 The continuous spectrum emitted
by the Sun passes through the
cooler gases of the Sun’s
atmosphere
 The various absorption lines can be
used to identify elements in the solar
atmosphere
 Led to the discovery of helium
Absorption Spectrum of
Hydrogen
 Neils Bohr
 1885 – 1962
 Participated in the early
development of
quantum mechanics
 Headed Institute in
Copenhagen
 1922 Nobel Prize for
structure of atoms and
radiation from atoms
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
 His model included an attempt to
explain why the atom was stable
 Bohr’s Assumptions for
Hydrogen
 The electron moves
in circular orbits
around the proton
under the influence
of the Coulomb force
of attraction
 The Coulomb force
produces the
centripetal
acceleration
Bohr’s Assumptions, cont
 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
 Radiation is emitted by the atom when
the electron “jumps” from a more
energetic initial state to a lower state
 The “jump” cannot be treated classically
Bohr’s Assumptions, final
 The electron’s “jump,” continued
 The frequency emitted in the “jump” is
related to the change in the atom’s energy
 It is generally not the same as the
frequency of the electron’s orbital motion
 The frequency is given by Ei – Ef = h ƒ
 The size of the allowed electron orbits is
determined by a condition imposed on
the electron’s orbital angular
momentum
Mathematics of Bohr’s
Assumptions and Results
 Electron’s orbital angular momentum
 me v r = n where n = 1, 2, 3, …
 The total energy of the atom

 The energy of the atom can also be

expressed as


 Bohr Radius
 The radii of the Bohr orbits are
quantized

 This is based on the assumption that the

electron can only exist in certain allowed
orbits determined by the integer n
 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 = n2 ao
 The energy of any
orbit is
 En = - 13.6 eV/ n2
 Specific Energy Levels
 The lowest energy state is called
the ground state
 This corresponds to n = 1
 Energy is –13.6 eV
 The next energy level has an
energy of –3.40 eV
 The energies can be compiled in an
energy level diagram
Specific Energy Levels,
cont
 The ionization energy is the energy
needed to completely remove the
electron from the atom
 The ionization energy for hydrogen is
13.6 eV
 The uppermost level corresponds
to E = 0 and n  
 Energy Level Diagram
 The value of RH from
Bohr’s analysis is in
excellent agreement
with the
experimental value
 A more generalized
equation can be used
to find the
wavelengths of any
spectral lines
Generalized Equation
 1 ⎛1 1⎞
= RH ⎜
⎜ 2
− 2 ⎟⎟
λ ⎝ n f ni ⎠
 For the Balmer series, nf = 2
 For the Lyman series, nf = 1
 Whenever an transition occurs between
a state, ni to another state, nf (where ni
> nf), a photon is emitted
 The photon has a frequency f = (Ei – Ef)/h
and wavelength 
Bohr’s Correspondence
Principle
 Bohr’s Correspondence Principle
states that quantum mechanics is
in agreement with classical physics
when the energy differences
between quantized levels are very
small
 Similar to having Newtonian
Mechanics be a special case of
relativistic mechanics when v << c
 Successes of the Bohr
Theory
 Explained several features of the hydrogen
spectrum
 Accounts for Balmer and other series
 Predicts a value for RH that agrees with the experimental
value
 Gives an expression for the radius of the atom
 Predicts energy levels of hydrogen
 Gives a model of what the atom looks like and how it
behaves
 Can be extended to “hydrogen-like” atoms
 Those with one electron
 Ze2 needs to be substituted for e2 in equations
 Z is the atomic number of the element
Modifications of the Bohr
Theory – Elliptical Orbits
 Sommerfeld extended the results to
include elliptical orbits
 Retained the principle quantum number, n
 Determines the energy of the allowed states
 Added the orbital quantum number, ℓ
 ℓ ranges from 0 to n-1 in integer steps
 All states with the same principle quantum
number are said to form a shell
 The states with given values of n and ℓ are
said to form a subshell
Modifications of the Bohr
Theory – Zeeman Effect
 Another modification was needed to
account for the Zeeman effect
 The Zeeman effect is the splitting of
spectral lines in a strong magnetic field
 This indicates that the energy of an electron
is slightly modified when the atom is
immersed in a magnetic field
 A new quantum number, mℓ, called the
orbital magnetic quantum number, had to
be introduced
 m ℓ can vary from - ℓ to + ℓ in integer steps
Modifications of the Bohr
Theory – Fine Structure
 High resolution spectrometers show
that spectral lines are, in fact, two very
closely spaced lines, even in the
absence of a magnetic field
 This splitting is called fine structure
 Another quantum number, ms, called the
spin magnetic quantum number, was
introduced to explain the fine structure
de Broglie Waves
 One of Bohr’s postulates was the
angular momentum of the electron is
quantized, but there was no explanation
why the restriction occurred
 de Broglie assumed that the electron
orbit would be stable only if it contained
an integral number of electron
wavelengths
de Broglie Waves in the
Hydrogen Atom
 In this example, three
complete wavelengths
are contained in the
circumference of the
orbit
 In general, the
circumference must
equal some integer
number of
wavelengths
 2  r = n  n = 1, 2, …
 de Broglie Waves in the
Hydrogen Atom, cont
 The expression for the de Broglie
wavelength can be included in the
circumference calculation
 me v r = n
 This is the same quantization of angular
momentum that Bohr imposed in his original
theory
 This was the first convincing argument
that the wave nature of matter was at
the heart of the behavior of atomic
systems
de Broglie Waves, cont.
 By applying wave theory to the
electrons in an atom, de Broglie was
able to explain the appearance of
integers in Bohr’s equations as a natural
consequence of standing wave patterns
 Schrödinger’s wave equation was
subsequently applied to atomic systems
Quantum Mechanics and
the Hydrogen Atom
 One of the first great achievements of
quantum mechanics was the solution of
the wave equation for the hydrogen
atom
 The significance of quantum mechanics
is that the quantum numbers and the
restrictions placed on their values arise
directly from the mathematics and not
from any assumptions made to make
the theory agree with experiments
Quantum Number
Summary
 The values of n can range from 1
to  in integer steps
 The values of ℓ can range from 0 to
n-1 in integer steps
 The values of m ℓ can range from -ℓ
to ℓ in integer steps
 Also see Table 28.2
 Spin Magnetic Quantum
Number
 It is convenient to think of
the electron as spinning on
its axis
 The electron is not
physically spinning
 There are two directions for
the spin
 Spin up, ms = 1/2
 Spin down, ms = -1/2
 There is a slight energy
difference between the two
spins and this accounts for
the doublet in some lines
Spin Notes
 A classical description of electron
spin is incorrect
 Since the electron cannot be located
precisely in space, it cannot be
considered to be a spinning solid
object
 P. A. M. Dirac developed a
relativistic quantum theory in
which spin appears naturally
 Electron Clouds
 The graph shows the
solution to the wave
equation for hydrogen in
the ground state
 The curve peaks at the
Bohr radius
 The electron is not confined
to a particular orbital
distance from the nucleus
 The probability of finding
the electron at the Bohr
radius is a maximum
 Electron Clouds, cont
 The wave function for
hydrogen in the ground
state is symmetric
 The electron can be found
in a spherical region
surrounding the nucleus
 The result is interpreted
by viewing the electron as
a cloud surrounding the
nucleus
 The densest regions of
the cloud represent the
highest probability for
finding the electron
Wolfgang Pauli
 1900 – 1958
 Contributions include
 Major review of
relativity
 Exclusion Principle
 Connect between
electron spin and
statistics
 Theories of relativistic
quantum
electrodynamics
 Neutrino hypothesis
 Nuclear spin hypothesis
The Pauli Exclusion
Principle
 No two electrons in an atom can
ever have the same set of values
of the quantum numbers n,ℓ, mℓ,
and ms
 This explains the electronic
structure of complex atoms as a
succession of filled energy levels
with different quantum numbers
Filling Shells
 As a general rule, the order that
electrons fill an atom’s subshell is:
 Once one subshell is filled, the next electron
goes into the vacant subshell that is lowest
in energy
 Otherwise, the electron would radiate
energy until it reached the subshell with the
lowest energy
 A subshell is filled when it holds 2(2ℓ+1)
electrons
 See table 28.3
The Periodic Table
 The outermost electrons are primarily
responsible for the chemical properties
of the atom
 Mendeleev arranged the elements
according to their atomic masses and
chemical similarities
 The electronic configuration of the
elements explained by quantum
numbers and Pauli’s Exclusion Principle
explains the configuration
 Characteristic X-Rays
 When a metal target is
bombarded by high-
energy electrons, x-rays
are emitted
 The x-ray spectrum
typically consists of a
broad continuous
spectrum and a series of
sharp lines
 The lines are dependent on
the metal of the target
 The lines are called
characteristic x-rays
Explanation of
Characteristic X-Rays
 The details of atomic structure can be
used to explain characteristic x-rays
 A bombarding electron collides with an electron
in the target metal that is in an inner shell
 If there is sufficient energy, the electron is
removed from the target atom
 The vacancy created by the lost electron is filled
by an electron falling to the vacancy from a
higher energy level
 The transition is accompanied by the emission of
a photon whose energy is equal to the difference
between the two levels
 Moseley Plot
  is the wavelength of the
K line
 K is the line that is
produced by an electron
falling from the L shell to
the K shell
 From this plot, Moseley was
able to determine the Z
values of other elements
and produce a periodic
chart in excellent
agreement with the known
chemical properties of the
elements
 Atomic Transitions –
Energy Levels
 An atom may have
many possible energy
levels
 At ordinary
temperatures, most of
the atoms in a sample
are in the ground state
 Only photons with
energies corresponding
to differences between
energy levels can be
absorbed
 Atomic Transitions –
Stimulated Absorption
 The blue dots
represent electrons
 When a photon with
energy E is
absorbed, one
electron jumps to a
higher energy level
 These higher levels are
called excited states
 E = hƒ = E2 – E1
 In general, E can be the
difference between any
two energy levels
 Atomic Transitions –
Spontaneous Emission
 Once an atom is in
an excited state,
there is a constant
probability that it will
jump back to a lower
state by emitting a
photon
 This process is called
spontaneous
emission
 Atomic Transitions –
Stimulated Emission
 An atom is in an excited
stated and a photon is
incident on it
 The incoming photon
increases the probability
that the excited atom will
return to the ground state
 There are two emitted
photons, the incident one
and the emitted one
 The emitted photon is in
exactly in phase with the
incident photon
Population Inversion
 When light is incident on a system of
atoms, both stimulated absorption and
stimulated emission are equally probable
 Generally, a net absorption occurs since
most atoms are in the ground state
 If you can cause more atoms to be in
excited states, a net emission of photons
can result
 This situation is called a population inversion
 Lasers
 To achieve laser action, three conditions
must be met
 The system must be in a state of population inversion
 More atoms in an excited state than the ground state
 The excited state of the system must be a metastable
state
 Its lifetime must be long compared to the normal
lifetime of an excited state
 The emitted photons must be confined in the system
long enough to allow them to stimulate further
emission from other excited atoms
 This is achieved by using reflecting mirrors
 Laser Beam – He Ne
Example
 The energy level diagram for
Ne in a He-Ne laser
 The mixture of helium and
neon is confined to a glass
tube sealed at the ends by
mirrors
 A high voltage applied causes
electrons to sweep through the
tube, producing excited states
 When the electron falls to E 2
from E*3 in Ne, a 632.8 nm
photon is emitted
Production of a Laser
Beam
 Holography
 Holography is the
production of three-
dimensional images of an
object
 Light from a laser is split at
B
 One beam reflects off the
object and onto a
photographic plate
 The other beam is diverged
by Lens 2 and reflected by
the mirrors before striking
the film
 Holography, cont
 The two beams form a complex interference
pattern on the photographic film
 It can be produced only if the phase relationship
of the two waves remains constant
 This is accomplished by using a laser
 The hologram records the intensity of the
light and the phase difference between the
reference beam and the scattered beam
 The image formed has a three-dimensional
perspective
Energy Bands in Solids
 In solids, the discrete energy
levels of isolated atoms broaden
into allowed energy bands
separated by forbidden gaps
 The separation and the electron
population of the highest bands
determine whether the solid is a
conductor, an insulator, or a
semiconductor
 Energy Bands, Detail
 Sodium example
 Blue represents energy bands
occupied by the sodium
electrons when the atoms are
in their ground states
 Gold represents energy bands
that are empty
 White represents energy gaps
 Electrons can have any
energy within the allowed
bands
 Electrons cannot have
energies in the gaps
Energy Level Definitions
 The valence band is the highest filled
band
 The conduction band is the next higher
empty band
 The energy gap has an energy, Eg,
equal to the difference in energy
between the top of the valence band
and the bottom of the conduction band
 Conductors
 When a voltage is applied to
a conductor, the electrons
accelerate and gain energy
 In quantum terms, electron
energies increase if there
are a high number of
unoccupied energy levels for
the electron to jump to
 For example, it takes very
little energy for electrons to
jump from the partially filled
to one of the nearby empty
states
 Insulators
 The valence band is
completely full of electrons
 A large band gap
separates the valence and
conduction bands
 A large amount of energy
is needed for an electron
to be able to jump from
the valence to the
conduction band
 The minimum required
energy is Eg
 Semiconductors
 A semiconductor has a
small energy gap
 Thermally excited electrons
have enough energy to
cross the band gap
 The resistivity of
semiconductors decreases
with increases in
temperature
 The white area in the
valence band represents
holes
Semiconductors, cont
 Holes are empty states in the valence band
created by electrons that have jumped to
the conduction band
 Some electrons in the valence band move to
fill the holes and therefore also carry current
 The valence electrons that fill the holes
leave behind other holes
 It is common to view the conduction process in
the valence band as a flow of positive holes
toward the negative electrode applied to the
semiconductor
 Movement of Charges in
Semiconductors
 An external voltage is
supplied
 Electrons move
toward the positive
electrode
 Holes move toward
the negative electrode
 There is a
symmetrical current
process in a
semiconductor
Doping in Semiconductors
 Doping is the adding of impurities
to a semiconductor
 Generally about 1 impurity atom per
107 semiconductor atoms
 Doping results in both the band
structure and the resistivity being
changed
n-type Semiconductors
 Donor atoms are doping materials that
contain one more electron than the
semiconductor material
 This creates an essentially free electron with
an energy level in the energy gap, just
below the conduction band
 Only a small amount of thermal energy
is needed to cause this electron to
move into the conduction band
 p-type Semiconductors
 Acceptor atoms are doping materials that
contain one less electron than the
semiconductor material
 A hole is left where the missing electron would be
 The energy level of the hole lies in the
energy gap, just above the valence band
 An electron from the valence band has
enough thermal energy to fill this impurity
level, leaving behind a hole in the valence
band
 A p-n Junction
 A p-n junction is
formed when a p-
type semiconductor
is joined to an n-
type
 Three distinct
regions exist
 A p region
 An n region
 A depletion region
 The Depletion Region
 Mobile donor electrons from the n side nearest
the junction diffuse to the p side, leaving
behind immobile positive ions
 At the same time, holes from the p side
nearest the junction diffuse to the n side and
leave behind a region of fixed negative ions
 The resulting depletion region is depleted of
mobile charge carriers
 There is also an electric field in this region that
sweeps out mobile charge carriers to keep the
region truly depleted
 Diode Action
 The p-n junction has the
ability to pass current in
only one direction
 When the p-side is
connected to a positive
terminal, the device is
forward biased and current
flows
 When the n-side is
connected to the positive
terminal, the device is
reverse biased and a very
small reverse current results
Applications of
Semiconductor Diodes
 Rectifiers
 Change AC voltage to DC voltage
 A half-wave rectifier allows current to flow during half
the AC cycle
 A full-wave rectifier rectifies both halves of the AC
cycle
 Transistors
 May be used to amplify small signals
 Integrated circuit
 A collection of interconnected transistors, diodes,
resistors and capacitors fabricated on a single piece
of silicon