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Chapter 42

Atomic Physics
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 Li2+
More Reasons the Hydrogen
Atom is Important
 The hydrogen atom proved to be 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
 This allows us to understand the periodic table
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 to the hydrogen
atom gives a complete and beautiful
description of the atom’s properties
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 for
atomic hydrogen
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
Emission Spectra Examples
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 spectrum of the light
source
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 can be calculated
Lyman series: 1  1
  RH  1  2  n  2, 3 , 4 ,K
λ  n 

1  1 1
 Paschen series:  RH  2  2  n  4 , 5 , 6 ,K
λ  3 n 
1  1 1
 Brackett series:  RH  2  2  n  5 , 6 , 7 ,K
λ  4 n 
Joseph John Thomson
 1856 – 1940
 Received Nobel Prize in
1906
 Usually considered the
discoverer of the
electron
 Worked with the
deflection of cathode
rays in an electric field
Early Models of the Atom
 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
Early Models of the Atom, 2
 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
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
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
 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 orbiting electrons
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 momentum quantization as
applied to atomic-sized systems
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
eventually spirals 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
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 nucleus is
quantized and equal to an integral
multiple of
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
k ee 2
E
2r
 Note, the total energy is negative, indicating a
bound electron-proton system
Bohr Radius
 The radii of the Bohr orbits are
quantized
n 2h2
rn  2
n  1, 2, 3 ,K
me kee
 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 = 0.0529 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, K
2ao  n 
 This becomes

En = - 13.606 eV/ n2
Active Figure 42.8

(SLIDESHOW MODE ONLY)


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
 The ionization energy for hydrogen is 13.6 eV
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
Frequency of Emitted Photons
 The frequency of the photon emitted
when the electron makes a transition
from an outer orbit to an inner orbit is
E i  Ef k e e 2  1 1
ƒ   2  2
h 2ao h  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 2ao hc  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 but one
electron had been removed
ao
rn   n 
2

Z
k ee 2  Z 2 
En    2  n  1, 2, 3 ,K
2ao  n 
 Z is the atomic number of the element
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 atom is
e2
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 and find the
appropriate solutions to the equations
 Because it is a three-dimensional
problem, it is easier to solve if the
rectangular coordinates are converted
to spherical polar coordinates
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 states in
the hydrogen atom are the same En
values found from the Bohr theory
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 describes the 1s state and is
designated ψ1s(r)
1
ψ1s (r )  e r ao
3
πa o

 As ψ1s(r) approaches zero, r approaches ∞


and is normalized as presented
 ψ1s(r) is also spherically symmetric
 This symmetry exists for all s states
Probability Density
 The probability density for the 1s state is

2  1  2r ao
ψ1s  3 
e
 πao 
 The radial probability density function P(r) is
the probability per unit radial length of finding
the electron in a spherical shell of radius r
and thickness dr
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 wave function is
3
1  1  2 r  r 2ao
ψ 2 s (r )     2  e
4 2π  ao   ao 

 ψ 2s 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 42.13

(SLIDESHOW MODE ONLY)


Physical Interpretation of ℓ
 The magnitude of the angular
momentum of an electron moving in a
circle of radius r is L = mevr
 The direction of L is perpendicular to
the plane of the circle
 In the Bohr model, the angular
momentum of the electron is restricted
to multiples of
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 values of
the magnitude of the orbital angular
momentum:
L  l l  1 h l  0 , 1, 2,K n  1
 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 angular
momentum
 There are distinct directions allowed for the
magnetic moment vector µ with respect to the
magnetic field vector B
Physical Interpretation of mℓ, 2
 Because the magnetic moment µ of the
atom can be related to the angular
momentum vector, L, the discrete
direction of µ translates into the fact that
the direction of L is quantized
 Therefore, Lz, the projection of L along
the z axis, can have only discrete
values
Physical Interpretation of mℓ, 3
 The orbital magnetic quantum number
mℓ specifies the allowed values of the z
component of orbital angular
momentum
 Lz = mℓ
 The quantization of the possible
orientations of L with respect to an
external magnetic field is often referred
to as space quantization
Physical Interpretation of mℓ, 4
 L does not point in a specific direction
 Even though its z-component is fixed
 Knowing all the components is inconsistent
with the uncertainty principle
 Imagine that L must lie anywhere 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 ml
cos θ  
L l 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
electron state contains both an orbital
contribution L and a spin contribution S
 Electron spin can be described by a single
quantum number s, whose value can only be
s=½
 The spin angular momentum of the electron
never changes
Spin Angular Momentum, cont
 The magnitude of the spin angular
momentum is
3
S  s(s  1)h  h
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
 ms = - ½ corresponds to the spin down case
Spin Angular Momentum, final
 The z component of
spin angular
momentum is Sz =
ms = ± ½
 Spin angular
moment S is
quantized
Spin Magnetic Moment
 The spin magnetic moment µspin is
related to the spin angular momentum
by e
μspin   S
me
 The z component of the spin magnetic
moment can have values
eh
μspin , z 
2me
Wolfgang Pauli
 1900 – 1958
 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
Filling Subshells
 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
Allowed Quantum States,
Example

 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
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 the gaps were there only
because the elements had not yet been
discovered
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
 The elements in the periodic table are
arranged so that all those in a column have
similar chemical properties
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 next available shell
Hydrogen Energy Level
Diagram Revisited
 The allowed values of ℓ
are separated
 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 a net
charge that is smaller than the nuclear
charge
2
13.6 Zeff
 Allowed energies are En   2
eV
n
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 nm to 1 nm
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 42.24

(SLIDESHOW MODE ONLY)


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
may also occur
 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
Lasers – Properties of
Laser Light
 Laser light is coherent
 The individual rays in a laser beam
maintain a fixed phase relationship with
each other
 There is no destructive interference
 Laser light is monochromatic
 The light has a very narrow range of
wavelengths
Lasers – Properties of
Laser Light, cont.
 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 can
result
 This condition is called population inversion
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

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