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PHYS2222
Quantum Physics
Reading list
For general reference the secondyear course book: Introduction to the Structure
of Matter by J.J. Brehm and W.J. Mullin (Wiley, 1989, ISBN 047160531X).
10 copies in UCL library, available from P&A Department. Referred to as B&M
in these notes.
Advantages: suitable for most 2
nd
year Physics courses, good integration of
quantum physics with atomic physics.
Disadvantages: weak on more formal aspects of quantum mechanics.
As a reasonably priced introduction: Quantum Mechanics by A.I.M. Rae (4
th
edition, Institute of Physics Publishing, 2002, ISBN 0 7503 0839 7).
9 copies in UCL library, available from P&A Department.
Advantages: cheap, well suited to level of course, covers essentially all the
material at roughly the right level.
Disadvantages: not so useful for other courses.
As a more advanced book that is also recommended for the thirdyear quantum
mechanics course: Quantum Mechanics by B.H. Bransden and C.J. Joachain (2
nd
edition, Prentice Hall, 2000, ISBN 0582356911).
10 copies in UCL library, available from P&A Department. Referred to as B&J
in these notes.
Advantages: material for 2222 is mostly presented at the start of the book.
Contains additional material going well beyond 2B22 for further reading. Useful
for both 3
rd
year and 4
th
year courses.
Disdavantages: coverage of some material (notably spin and emission/absorption
of radiation) is at a more advanced level than 2222 and is not so useful for this
course. Relatively expensive (£41 on Amazon).
2222 Quantum Physics 20067 2
Prerequisites
Firstyear Mathematics for Physics and Astronomy (1B45
and 1B46) or equivalent
Material from the secondyear maths course (2246) will be
used after it has been covered in that course
Basic relativistic kinematics (from 1B46) will be assumed,
and basic electromagnetism (field and potential of point
charge, interaction of magnetic dipole with magnetic field)
will be used as it is covered in 2201
2222 and other courses
Some limited overlap with 1B23 Modern Physics,
Astronomy and Cosmology (bur different approach – 2222
is less descriptive and more rigorous). Areas covered by
both courses:
o Waveparticle duality (photoelectric effect, double
slit experiment)
o Timeindependent Schrődinger equation
o Significance of wave function and Heisenberg’s
Uncertainty Principle
1B23 is not a prerequisite for 2222!
2222 Quantum Physics 20067 3
Syllabus
1. The failure of classical mechanics [3 lectures]
Photoelectric effect, Einstein’s equation, electron diffraction and de Broglie relation.
Compton scattering. Waveparticle duality, Uncertainty principle (Bohr microscope).
2. Steps towards wave mechanics [3 lectures]
Timedependent and timeindependent Schrödinger equations. The wave function and its
interpretation.
3. Onedimensional timeindependent problems [7 lectures]
Infinite square well potential. Finite square well. Probability flux and the potential barrier
and step. Reflection and transmission. Tunnelling and examples in physics and
astronomy. Wavepackets. The simple harmonic oscillator.
4. The formal basis of quantum mechanics [5 lectures]
The postulates of quantum mechanics – operators, observables, eigenvalues and
eigenfunctions. Hermitian operators and the Expansion Postulate.
5. Angular momentum in quantum mechanics [2 lectures]
Operators, eigenvalues and eigenfunctions of
ˆ
L
z
and
ˆ
L
2
.
2222 Quantum Physics 20067 4
Syllabus (contd)
6. Three dimensional problems and the hydrogen atom [4 lectures]
Separation of variables for a threedimensional rectangular well. Separation of space and time
parts of the 3D Schrödinger equation for a central field. The radial Schrödinger equation, and
casting it in a form suitable for solution by series method. Degeneracy and spectroscopic
notation.
7. Electron spin and total angular momentum [3 lectures]
Magnetic moment of electron due to orbital motion. The SternGerlach experiment. Electron
spin and complete set of quantum numbers for the hydrogen atom. Rules for addition of
angular momentum quantum numbers. Total spin and orbital angular momentum quantum
numbers S, L, J. Construct J from S and L.
2222 Quantum Physics 20067 5
Photoelectric effect, Compton
scattering
DavissonGermer experiment, double
slit experiment
Particle nature of light in
quantum mechanics
Wave nature of matter in quantum
mechanics
Waveparticle duality
Timedependent Schrödinger equation,
Born interpretation
2246 Maths
Methods III
Timeindependent Schrödinger
equation
Quantum simple
harmonic oscillator
Hydrogenic atom 1D problems
Radial solution
2
2
1
,
2
nl
Z
R E
n
·
Angular solution
( , )
m
l
Y u o
Postulates:
Operators,eigenvalues and
eigenfunctions, expansions in
complete sets, commutators,
expectation values, time
evolution
Angular momentum
operators
2
ˆ ˆ
,
z
L L
E hv ·
h
p
i
·
2246
Frobenius
method
Separation of variables
Legendre
equation
E
n
=
¦
n+
1
2
)
ℏ o
0
2222 Quantum Physics 20067 6
Lecture style
• Experience (and feedback) suggests the biggest problems found by
students in lectures are:
– Pacing of lectures
– Presentation and retention of mathematically complex material
• Our solution for 2222:
– Use powerpoint presentation via data projector or printed OHP for written
material and diagrams
– Use whiteboard or handwritten OHP for equations in all mathematically
complex parts of the syllabus
– Student copies of notes will require annotation with these mathematical
details
– Notes (unannotated) will be available for download via website or (for a
small charge) from the Physics & Astronomy Office
• Headings for sections relating to key concepts are marked with
asterisks (***)
2222 Quantum Physics 20067 7
1.1 Photoelectric effect
B&M §2.5; Rae §1.1;
B&J §1.2
Metal plate in a vacuum, irradiated by ultraviolet light, emits
charged particles (Hertz 1887), which were subsequently shown
to be electrons by J.J. Thomson (1899).
Electric field E of light exerts force F=
eE on electrons. As intensity of light
increases, force increases, so KE of
ejected electrons should increase.
Electrons should be emitted whatever
the frequency ν of the light, so long as E
is sufficiently large
For very low intensities, expect a time lag
between light exposure and emission,
while electrons absorb enough energy to
escape from material
Classical expectations
Hertz J.J. Thomson
I
Vacuum
chamber
Metal
plate
Collecting
plate
Ammeter
Potentiostat
Light, frequency ν
2222 Quantum Physics 20067 8
Photoelectric effect (contd)***
(1.1) E hv ·
The maximum KE of an emitted electron is then predicted to be:
Maximum KE of ejected electrons is
independent of intensity, but
dependent on ν
For ν<ν
0
(i.e. for frequencies below
a cutoff frequency) no electrons
are emitted
There is no time lag. However, rate
of ejection of electrons depends on
light intensity.
Einstein’s
interpretation (1905):
light is emitted and
absorbed in packets
(quanta) of energy
max
(1.2) K h W v ·
Work function: minimum energy
needed for electron to escape
from metal (depends on
material, but usually 25eV)
Planck constant:
universal constant of
nature
Einstein
Millikan
Verified in detail
through
subsequent
experiments by
Millikan
Actual results:
An electron absorbs a
single quantum in
order to leave the
material
h=6.63×10
−34
Js
2222 Quantum Physics 20067 9
Photoemission experiments today
Modern successor to original photoelectric
effect experiments is ARPES (Angle
Resolved Photoemission Spectroscopy)
Emitted electrons give information on
distribution of electrons within a material as
a function of energy and momentum
2222 Quantum Physics 20067 10
Frequency and wavelength for
light***
2 2 2 2 4
0
E p c m c · +
Relativistic relationship between a
particle’s momentum and energy:
For massless particles
propagating at the speed of light,
becomes
2 2 2
E p c ·
Hence find relationship
between momentum p and
wavelength λ:
E=c∣ p∣
h+=c∣ p∣
∣ p∣=
h+
c
\+=c
∣ p∣=
h
\
But:
(For light.)
2222 Quantum Physics 20067 11
1.2 Compton scattering
Xray source
Target
Crystal
(selects
wavelength)
Collimator
(selects angle)
θ
Compton (1923) measured scattered intensity of Xrays (with welldefined wavelength)
from solid target, as function of wavelength for different angles.
Result: peak in the wavelength
distribution of scattered radiation shifts to
longer wavelength than source, by an
amount that depends on the scattering
angle θ (but not on the target material)
A.H. Compton, Phys.
Rev. 22 409 (1923)
Detector
B&M §2.7; Rae §1.2;
B&J §1.3
Compton
2222 Quantum Physics 20067 12
Compton scattering (contd)
Compton’s explanation: “billiard ball” collisions between
Xray photons and electrons in the material
Conservation of energy: Conservation of momentum:
θ
φ
p’
Classical picture: oscillating electromagnetic field would cause oscillations
in positions of charged particles, reradiation in all directions at same
frequency and wavelength as incident radiation
p
Electron
Incoming photon
Before
After
p
e
Photon
Frequency
+
h++m
e
c
2
=h+' +¦ p
e
2
c
2
+m
e
2
c
4
)
1
2
Write in terms of momentum:
pc+m
e
c
2
=p' c+¦ p
e
2
c
2
+m
e
2
c
4
)
1
2
¦ p−p' ) c+m
e
c
2
=¦ p
e
2
c
2
+m
e
2
c
4
)
1
2
¦ p−p' )
2
c
2
+m
e
2
c
4
+2¦ p−p' ) m
e
c
3
=p
c
2
+m
e
2
c
4
¦ p−p' )
2
+2¦ p−p' ) m
e
c=p
e
2
In electrons initial rest frame:
p=p' +p
e
p
e
=p−p'
∣
p
e
2
∣
=¦ p−p' ). ¦ p−p' )=∣ p
2
∣+∣ p '
2
∣−2∣ p∣∣ p'∣ cos0
∣
p
e
2
∣
=¦ p−p' )
2
+2¦1−cos 0) pp '
2222 Quantum Physics 20067 13
Compton scattering (contd)
(1.3)
h
p
i
·
Assuming photon
momentum related to
wavelength:
' (1 cos ) (1.4)
e
h
m c
i i u ·
‘Compton wavelength’
of electron (0.0243 Å)
Equate above for p
e
2
:
¦ p−p' )
2
+2¦ p−p' ) m
e
c=¦ p−p' )
2
+2¦1−cos0) pp'
⇒¦ p−p' ) m
e
c=¦1−cos0) pp'
⇒m
e
c¦
1
p'
−
1
p
)=1−cos0
⇒
m
e
c
h
¦\' −\)=1−cos0
2222 Quantum Physics 20067 14
Puzzle
What is the origin of the component of
the scattered radiation that is not
wavelengthshifted?
Second peak at original due
to nuclei collisions.
Substitute: −
ℏ
2
2m
\
2
e
\x
=Ee
\x
⇒ −
ℏ
2
2m
\
2
=E ⇒ \
2
=−
2mE
ℏ
2
⇒ Assuming E¯0 RHSis ve \ is imaginary.
\=!ik where k
2
=
2mE
ℏ
2
or
ℏ
2
k
2
2m
=E k is DeBroglie wavenumber. p=ℏ k
2222 Quantum Physics 20067 15
Waveparticle duality for light***
“ There are therefore now two theories of light, both indispensable, and  as one
must admit today despite twenty years of tremendous effort on the part of
theoretical physicists  without any logical connection.” A. Einstein (1924)
•Light exhibits diffraction and interference phenomena that
are only explicable in terms of wave properties
•Light is always detected as packets (photons); if we look, we
never observe half a photon
•Number of photons proportional to energy density (i.e. to
square of electromagnetic field strength)
2222 Quantum Physics 20067 16
1.3 Matter waves***
“As in my conversations with my brother we always arrived at the conclusion that in
the case of Xrays one had both waves and corpuscles, thus suddenly  ... it was
certain in the course of summer 1923  I got the idea that one had to extend this
duality to material particles, especially to electrons. And I realised that, on the one
hand, the HamiltonJacobi theory pointed somewhat in that direction, for it can be
applied to particles and, in addition, it represents a geometrical optics; on the other
hand, in quantum phenomena one obtains quantum numbers, which are rarely found
in mechanics but occur very frequently in wave phenomena and in all problems
dealing with wave motion.” L. de Broglie
De Broglie
Proposal: dual waveparticle nature of radiation
also applies to matter. Any object having
momentum p has an associated wave whose
wavelength λ obeys
Prediction: crystals
(already used for X
ray diffraction) might
also diffract particles
2
(wavenumber) k
r
i
·
B&M §4.12; Rae §1.4;
B&J §1.6
¦
ℏ=
h
2n
)
p=
h
\
=ℏ k
2222 Quantum Physics 20067 17
Electron diffraction from crystals
Davisson G.P. Thomson
Davisson, C. J.,
"Are Electrons
Waves?," Franklin
Institute Journal
205, 597 (1928)
The DavissonGermer experiment
(1927): scattering a beam of
electrons from a Ni crystal
At fixed accelerating voltage (i.e. fixed
electron energy) find a pattern of pencil
sharp reflected beams from the crystal
At fixed angle, find sharp peaks in intensity
as a function of electron energy
G.P. Thomson performed similar interference
experiments with thinfilm samples
θ
i
θ
r
2222 Quantum Physics 20067 18
Electron diffraction from crystals
(contd)
Modern Low Energy
Electron Diffraction
(LEED): this pattern of
“spots” shows the beams
of electrons produced by
surface scattering from
complex (7×7)
reconstruction of a silicon
surface
Lawrence
Bragg
William Bragg
(Quain Professor
of Physics, UCL,
19151923)
Interpretation used similar ideas to those pioneered for scattering
of Xrays from crystals by William and Lawrence Bragg
a
θ
i
θ
r
cos
i
a u
cos
r
a u
Path difference:
Constructive interference when
Note difference from usual “Bragg’s
Law” geometry: the identical scattering
planes are oriented perpendicular to
the surface
Note θ
i
and θ
r
not
necessarily equal
Electron scattering
dominated by surface
layers
acos 0
r
−a cos0
i
a¦cos 0
r
−cos0
i
)
a¦cos 0
r
−cos0
i
)=n\
2222 Quantum Physics 20067 19
The doubleslit interference
experiment
sin d u
Originally performed by Young (1801) with light. Subsequently also performed
with many types of matter particle (see references).
D
θ
d
Detecting
screen
(scintillators or
particle
detectors)
Incoming beam of
particles (or light)
y
Alternative method
of detection: scan
a detector across
the plane and
record arrivals at
each point
2222 Quantum Physics 20067 20
Results
Neutrons, A
Zeilinger et al. 1988
Reviews of Modern
Physics 60 1067
1073
He atoms: O Carnal and J Mlynek
1991 Physical Review Letters 66
26892692
C
60
molecules: M
Arndt et al. 1999
Nature 401 680
682
With multiple
slit grating
Without grating
Fringe visibility
decreases as
molecules are
heated. L.
Hackermüller et
al. 2004 Nature
427 711714
2222 Quantum Physics 20067 21
Doubleslit experiment: interpretation
Interpretation: maxima and minima arise from alternating constructive and
destructive interference between the waves from the two slits
Spacing between maxima:
Example: He atoms at a temperature
of 83K, with d=8μm and D=64cm
Constructive interference:
d sin 0=n\
⇒n
th
maximum occurs at:
d sin 0
n
=n\
For small 0 , sin 0≈tan 0
0
n
≈
n\
d
⇒Maximum at y
n
=Dtan 0
n
≈D0
n
≈
n\ D
d
⇒Spacing at
\ D
d
Expect:
p
2
2m
=
3
2
K
B
T ⇒ p=4.8×10
−24
Ns⇒\=
h
p
=1.03 Å
⇒ Spacing =
\ D
d
=8.24×10
−6
m
2222 Quantum Physics 20067 22
Doubleslit experiment: bibliography
Some key papers in the development of the doubleslit experiment during the
20
th
century:
• Performed with a light source so faint that only one photon exists in the
apparatus at any one time (G I Taylor 1909 Proceedings of the Cambridge
Philosophical Society 15 114115)
• Performed with electrons (C Jönsson 1961 Zeitschrift für Physik 161 454
474, translated 1974 American Journal of Physics 42 411)
• Performed with single electrons (A Tonomura et al. 1989 American Journal
of Physics 57 117120)
• Performed with neutrons (A Zeilinger et al. 1988 Reviews of Modern
Physics 60 10671073)
• Performed with He atoms (O Carnal and J Mlynek 1991 Physical Review
Letters 66 26892692)
• Performed with C
60
molecules (M Arndt et al. 1999 Nature 401 680682)
• Performed with C
70
molecules, showing reduction in fringe visibility as
temperature rises so molecules “give away” their position by emitting
photons (L. Hackermüller et al. 2004 Nature 427 711714)
An excellent summary is available in Physics World (September 2002 issue,
page 15) and at http://physicsweb.org/ (readers voted the doubleslit
experiment “the most beautiful in physics”).
2222 Quantum Physics 20067 23
Matter waves: key points***
• Interference occurs even when only a single particle (e.g. photon or electron) in
apparatus, so wave is a property of a single particle
– A particle can “interfere with itself”
• Wavelength unconnected with internal lengthscales of object, determined by
momentum
• Attempt to find out which slit particle moves through causes collapse of
interference pattern (see later…)
•Particles exhibit diffraction and interference phenomena that
are only explicable in terms of wave properties
•Particles always detected individually; if we look, we never
observe half an electron
•Number of particles proportional to….???
Waveparticle duality for matter particles
2222 Quantum Physics 20067 24
1.4 Heisenberg’s gammaray microscope and a first look at the
Uncertainty Principle
y A
The combination of wave and particle pictures, and in particular the significance of
the ‘wave function’ in quantum mechanics (see also §2), involves uncertainty: we
only know the probability that the particle will be found near a particular location.
θ/2
Light source,
wavelength λ
Particle
Lens, having angular
diameter θ
Screen forming
image of particle
Resolving power of lens:
Heisenberg
B&M §4.5; Rae §1.5; B&J §2.5 (first part only)
Ay¯
\
0
2222 Quantum Physics 20067 25
Heisenberg’s gammaray microscope and the Uncertainty
Principle***
Range of ymomenta of photons after
scattering, if they have initial momentum p:
θ/2
p
p
Heisenberg’s Uncertainty
Principle
Ycomponent of momentum
after scattering.
−psin
¦
0
2
)
p
y
+psin
¦
0
2
)
⇒ Partice momentum must lie
in the same range:
A p
y
=2psin
¦
0
2
)
≃p0
Remember resolution power of
lens from classical optics:
A y¯
\
0
Ay A p
y
¯h
(Assuming magnitude of
p unchanged i.e.
Neglecting Compton
effect.)
(Small angle/small lens)
p
x
P
y
Ay A p
y
¯h
2222 Quantum Physics 20067 26
2.1 An equation for the matter waves: the time
dependent Schrődinger equation***
( , ) x t +
wave velocity v ·
Classical wave equation (in
one dimension):
Can we use this to describe the
matter waves in free space?
e.g. Transverse waves on
a string:
x
( , ) wave displacement (in 1d) x t + ·
Rae §2.1, B&J §3.1, B&M §5.1
6
2
1
6 x
2
=
1
+
2
6
2
1
6t
2
2222 Quantum Physics 20067 27
An equation for the matter waves (2)
Seem to need an equation that
involves the first derivative in
time, but the second derivative in
space
(for matter waves in free space)
( , ) is "wave function" associated with matter wave x t +
Put: 1¦ x , t )=Ae
i ¦ kx−ot )

d
2
1
dx
2
=−k
2
Ae
i ¦kx−ot )
;
d 1
dt
=−i oAe
i ¦ kx−ot )
⇒−i oo=−k
2
We want the energy to be
p
2
2m
⇒ ℏ o=
¦ℏ k)
2
2m
So choose o so this is true.
⇒−i o
ℏk
2
2m
=−k
2
⇒o=
2m
i ℏ
So, wave equation is:
2m
i ℏ
d 1
dt
=
d
2
1
dx
2
¦
Multiplying bothsides by
−ℏ
2
2m
)
Try: o
61
6t
=
6
2
1
6 x
2
i ℏ
61
6t
=−
ℏ
2
2m
6
2
1
6 x
2
2222 Quantum Physics 20067 28
An equation for the matter waves (3)
2
( , )
2
p
E V x t
m
· +
For particle with potential energy V(x,t),
need to modify the relationship between
energy and momentum:
Suggests corresponding modification to
Schrődinger equation:
Timedependent Schrődinger equation
Total energy = kinetic energy + potential energy
Schrődinger
We had: i ℏ
d 1
dt
=
−ℏ
2
2m
d
2
1
dx
2
LHS: Gives ℏo1 for a plane wave.
RHS: Gives
¦ℏ k)
2
2m
1 for a plane wave.
⇒Try adding a term V ¦ x , t )1 on RHS.
i ℏ
61
6t
=−
ℏ
2
2m
6
2
1
6 x
2
+V ¦ x , t )1
2222 Quantum Physics 20067 29
The Schrődinger equation: notes
•This was a plausibility argument, not a derivation. We believe the Schrődinger
equation to be true not because of this argument, but because its predictions agree
with experiment.
•There are limits to its validity. In this form it applies to
•A single particle, moving in one direction, that is
•Nonrelativistic (i.e. has nonzero rest mass and velocity very much below c)
•The Schrődinger equation is a partial differential equation in x and t (like classical
wave equation)
•The Schrődinger equation contains the complex number i. Therefore its solutions
are essentially complex (unlike classical waves, where the use of complex numbers
is just a mathematical convenience)
•Positive i is merely a convention.
2222 Quantum Physics 20067 30
The Hamiltonian operator
Can think of the RHS of the Schrődinger equation as a
differential operator that represents the energy of the
particle.
This operator is called the Hamiltonian of the
particle, and usually given the symbol
Hence there is an alternative (shorthand) form
for timedependent Schrődinger equation:
ˆ
H
Kinetic
energy
operator
Potential
energy
operator
i ℏ
61
6t
=−
ℏ
2
2m
6
2
1
6 x
2
+V ¦ x , t )1
[
−
ℏ
2
2m
d
2
d x
2
+V ¦ x , t )

1≡
´
H 1
i ℏ
61
6t
=
´
H1
2222 Quantum Physics 20067 31
2.2 The significance of the wave function***
2
*
+ · + +
2
( , ) (2.6) x t x ô +
Ψ is a complex quantity, so what can be its significance for the results
of real physical measurements on a system?
Remember photons: number of photons per unit volume is
proportional to the electromagnetic energy per unit volume,
hence to square of electromagnetic field strength.
Postulate (Born interpretation): probability of finding particle in a small
length δx at position x and time t is equal to
Note: Ψ(x,t)
2
is real, so probability is also real, as required.
Total probability of finding particle between
positions a and b is
a b
Ψ
2
x
δx
Born
Rae §2.1, B&J §2.2, B&M §5.2
∑
x=a
b
∣1¦ x , t )∣
2
6 x 6 x 0
∫
a
b
∣1¦ x , t )∣
2
dx
2222 Quantum Physics 20067 32
Example
Suppose that at some instant of time a particle’s wavefunction is
What is:
(a) The probability of finding
the particle between x=0.5 and
x=0.5001?
(b) The probability per unit
length of finding the particle
at x=0.6?
(c) The probability of finding
the particle between x=0.0 and
x=0.5?
Probability: ∣1∣
2
6 x
With: x=0.5, 1=1, ⇒ ∣1∣
2
=1
⇒ Probability =1 x 10
−4
Probability for unit length: ∣1∣
2
= 1.44
Total probability =
∫
0
0.5
∣1∣
2
6 x
=
∫
0
0.5
4x
2
6 x=0.167
1¦ x , t )
¦
2x (For 0<x<0.909)
0 (Otherwise)
¦
2222 Quantum Physics 20067 33
Normalization
Total probability for particle to be anywhere should be one (at
any time):
Suppose we have a solution to the
Schrődinger equation that is not
normalized, Then we can
•Calculate the normalization integral
•Rescale the wave function as
(This works because any solution to the
S.E., multiplied by a constant, remains a
solution, because the equation is linear and
homogeneous)
Normalization condition
Alternatively: solution to Schrödinger equation contains an arbitrary
constant, which can be fixed by imposing the condition (2.7)
N=
∫
−∞
∞
∣1∣
2
6 x
1¦ x , t )N
−
1
2
1¦ x , t )
So:
∫
−∞
∞
∣
1
new
∣
2
6 x=
∫
−∞
∞
∣1∣
2
N
6 x
=
N
N
=1
∫
−∞
∞
∣1¦ x , t )∣
2
dx=1
2222 Quantum Physics 20067 34
Normalizing a wavefunction  example
Suppose that at some time we have the following form to the wavefunction:
1¦ x , t )
¦
.
a
2
−x
2
for −a<x<a
0 otherwise
¦
1
x a −a
Normalisation integral:
N=
∫
−∞
∞
∣1¦ x , t )∣
2
6 x=
∫
−a
a
1¦ x , t )
2
=
∫
−a
a
¦a
2
−x
2
)6 x=
[
a
2
x−
x
3
3

−a
a
=
2a
3
3
−
¦
−
2a
3
3
)
=
4a
3
3
This is not, in general, equal to
1. Therefore is not correctly
normalised. To get a correctly
normalised wavefunction, take:
1¦ x , t )=
.
3a
3
4
. a
2
−x
2
2222 Quantum Physics 20067 35
2.3 Boundary conditions for the wavefunction
The wavefunction must:
1. Be a continuous and singlevalued function
of both x and t (in order that the probability
density be uniquely defined)
2. Have a continuous first derivative (unless the
potential goes to infinity)
3. Have a finite normalization integral.
Rae §2.3, B&J §3.1
1
x
1
x
1
x
Multivalued.
Unacceptable
Discontinuous.
Discontinuous.
Change in
d 1
dx
only
allowed if potential !∞
0
∫
−∞
∞
∣1∣
2
6 x∞
2222 Quantum Physics 20067 36
2.4 Timeindependent Schrődinger
equation***
Suppose potential V(x,t) (and hence force on
particle) is independent of time t:
LHS involves only
variation of Ψ with t
RHS involves only variation of Ψ with
x (i.e. Hamiltonian operator does not
depend on t)
Look for a solution in which the time and
space dependence of Ψ are separated:
Substitute:
Rae §2.2, B&J §3.5, B&M §5.3
i ℏ1¦ x , t )
dT
dt
=−
ℏ
2
2m
T ¦t )
d
2
1
dx
2
+V ¦ x)m¦ x)T ¦t )
Divide by 1¦ x) T ¦t ) :
i ℏ
T
dT
dt
=−
ℏ
2
2m1
d
2
1
dx
2
+V ¦ x)
i ℏ
T
dT
dt
=−
ℏ
2
2m1
d
2
1
dx
2
+V ¦ x)=E
Independent
of position x.
Independent of
time t.
Equal to constant
E as both sides are
independent of
each other.
i ℏ
61
6t
=−
ℏ
2
2m
6
2
1
6 x
2
+V ¦ x)1
1¦ x , t )=m¦ x)T ¦t )
2222 Quantum Physics 20067 37
Timeindependent Schrődinger equation
(contd)
Solving the time equation:
The space equation becomes:
Timeindependent Schrődinger equation
i ℏ
T
dT
dt
=E ⇒ i ℏ
dT
dt
=ET
Linear ordinary differential equation with constant coefficients.
Try: T =Ae
\t
⇒ Substitute.
i ℏ\=E ⇒ \=−
i E
ℏ
Solution is: T ¦t )=e
−
iEt
ℏ
−
ℏ
2
2m1
d
2
1
dx
2
+V ¦ x)=E
Now multiply by 1 to get the final version.
−
ℏ
2
2m
d
2
m
d x
2
+V ¦ x) m=Em or
´
Hm=Em
2222 Quantum Physics 20067 38
Notes
• In one space dimension, the timeindependent Schrődinger equation is an
ordinary differential equation (not a partial differential equation)
• The sign of i in the time evolution is determined by the choice of the sign of i in
the timedependent Schrődinger equation
• The timeindependent Schrődinger equation can be thought of as an eigenvalue
equation for the Hamiltonian operator:
Operator × function = number × function
(Compare Matrix × vector = number × vector) [See 2246]
• We will consistently use uppercase Ψ(x,t) for the full wavefunction (time
dependent Schrődinger equation), and lowercase ψ(x) for the spatial part of the
wavefunction when time and space have been separated (timeindependent
Schrődinger equation)
• Probability distribution of particle is now independent of time (“stationary
state”):
ˆ
H E v v ·
For a stationary state we can use
either ψ(x) or Ψ(x,t) to compute
probabilities; we will get the same
result.
∣1¦ x , t )∣
2
=
∣
e
−i E t
ℏ
m¦ x)
∣
2
=
∣
e
−i E t
ℏ
∣
2
∣m¦ x)∣
2
=∣m¦ x)∣
2
2222 Quantum Physics 20067 39
2.6 SE in three dimensions
ˆ
H E v v ·
To apply the Schrődinger equation in the real (threedimensional)
world we keep the same basic structure:
BUT
Wavefunction and potential energy are now
functions of three spatial coordinates:
Kinetic energy now involves three
components of momentum
Interpretation of wavefunction:
Rae §3.1, B&J §3.1, B&M §5.1
1¦ x , t )  1¦ x , y , z , t ) or 1¦r , t )
m¦ x)  m¦ x , y , z) or m¦r )
V ¦ x)  V ¦ x , y , z , t )or V ¦ r )
p
2
2m

p
x
2
+p
y
2
+p
z
2
2m
⇒ −
ℏ
2
2m
6
2
6 x
2
 −
ℏ
2
2m[
6
2
6 x
2
+
6
2
6 y
2
+
6
2
6 z
2

=−
ℏ
2
2m
∇
2
∣1¦ x , y , z , t )∣
2
6V =
Probability of finding particle
in a small volume dV around
(x, y, z)
⇒∣1∣
2
=
Probability per unit
volume.
i ℏ
61
6t
=
´
H1
2222 Quantum Physics 20067 40
Puzzle
( , ) exp[ ( )] x t i kx t u + ·
2 2 2 2 4
0
E p c m c · +
The requirement that a plane wave
plus the energymomentum relationship for freenonrelativistic particles
led us to the freeparticle Schrődinger equation.
Can you use a similar argument to suggest an equation for free relativistic
particles, with energymomentum relationship:
2
2
p
E
m
·
Einstein: E=ℏo DeBroglie: p=ℏ k
E
2
1=−
6
2
1
6t
2
ℏ
2
p
2
1=−
6
2
1
6 x
2
ℏ
2
⇒Try: −ℏ
2
6
2
1
6t
2
=−ℏ
2
c
2
6
2
1
6 x
2
+m
0
2
c
4
1
(KleinGordon equation.)
2222 Quantum Physics 20067 41
3.1 A Free Particle
Free particle: experiences no forces so potential energy independent
of position (take as zero)
Timeindependent Schrődinger
equation:
Linear ODE with
constant coefficients so
try
exp( ) x v i ·
General solution:
Substitute: −
ℏ
2
2m
\
2
e
\ x
=Ee
\x
⇒ −
ℏ
2
2m
\
2
=E ⇒ \
2
=−
2mE
ℏ
2
⇒ Assuming E¯0 RHS is ve \ is imaginary.
\=!ik where k
2
=
2mE
ℏ
2
or
ℏ
2
k
2
2m
=E k is DeBroglie wavenumber. p=ℏ k
m¦ x)=Ce
ikx
+De
−ikx
( C and D are constants.)
= C¦cos¦kx)+i sin¦ kx))+D¦cos¦ kx)−i sin¦ kx))
= Acos¦ kx)+Bsin¦ kx) where: A=C+D , B=i ¦C−D)
−
ℏ
2
2m
d
2
m
d x
2
=Em
2222 Quantum Physics 20067 42
3.1 A Free Particle (Cont.)
Combine with time dependence to
get full wave function:
1¦ x , t )=m¦ x)e
iEt
ℏ
=¦Ce
ikx
+De−ikx) e
i
Et
ℏ
1 = C e
i ¦kx−
Et
ℏ
)
+ De
i ¦kx−
Et
ℏ
)
Travelling wave
moving to the right.
Travelling wave
moving to the left.
+t  +x +t  −x
2222 Quantum Physics 20067 43
Notes
• Plane wave is a solution (just as well, since our plausibility
argument for the Schrődinger equation was based on this
being so)
• Note signs:
– Sign of time term (iωt) is fixed by sign adopted in timedependent
Schrődinger Equation
– Sign of position term (±ikx) depends on propagation direction of
wave
• There is no restriction on the allowed energies, so there is a
continuum of states
2222 Quantum Physics 20067 44
3.2 Infinite Square Well
Consider a particle confined to a finite
length –a<x<a by an infinitely high
potential barrier
V(x)
x
a a
0 V ·
No solution in barrier region (particle would
have infinite potential energy).
In well region:
Rae §2.4, B&J §4.5,
B&M §5.4
Boundary conditions:
Continuity of ψ at x=a:
Continuity of ψ at x=a:
Note discontinuity in dψ/dx
allowable, since potential
is infinite
−
ℏ
2
2m
6
2
m
6 x
2
=Em As for free particle.
⇒m¦ x)=Acos¦ kx)+Bsin¦kx) With: k
2
=
2mE
ℏ
2
m¦ a)=0⇒Acos¦ ka)+Bsin¦ ka)=0
m¦−a)=0⇒Acos ¦−ka)+Bsin¦−ka)=0
or Acos¦ ka)−Bsin¦ ka)=0
¦
Since:
cos¦−!)=cos¦!)
Even function.
sin¦−!)=−sin¦!)
Odd function.
)
V=∞ V=∞
2222 Quantum Physics 20067 45
Infinite square well (2)
Add and subtract these
conditions:
Even solution: ψ(x)=ψ(x)
Odd solution: ψ(x)=ψ(x)
Energy:
Adding gives: 2Acos¦ ka)=0
Subtracting gives: 2Bsin¦ ka)=0
Either, a) Put B=0 and cos¦ ka)=0
⇒ka=
nn
2
¦ n=1, 3,5, 7. ...)
⇒k=
nn
2a
, m¦ x)=Acos¦ kx)
Or, b) Put A=0 and sin¦ ka)=0
⇒ka=
nn
2
¦n=2, 4, 6,8. ...)
⇒k=
nn
2a
, m¦ x)=Bsin¦ kx)
Same Schrödinger equation for particle in box as for particle in free space.
→ Same relation between E and k.
⇒E=
ℏ
2
k
2
2m
=
n
2
n
2
ℏ
2
2m¦2a)
2
E=
n
2
n
2
ℏ
2
8ma
2
2222 Quantum Physics 20067 46
Infinite well – normalization and notes
Notes on the solution:
• Energy quantized to particular values (characteristic of boundstate problems in quantum
mechanics, where a particle is localized in a finite region of space.
• Potential is even under reflection; stationary state wavefunctions may be even or odd (we say
they have even or odd parity)
• Compare notation in 1B23 and in books:
– 1B23: well extended from x=0 to x=b
– Rae and B&J: well extends from x=a to x=+a (as here)
– B&M: well extends from x=a/2 to x=+a/2
(with corresponding differences in wavefunction)
Normalization:
Need to choose constants so is normalised. (i.e: Total over integral is 1).
Even soln.
∫
−a
a
∣m∣
2
6 x=1⇒
∫
−a
a
∣ A∣
2 1
2
[1+cos¦2kx)6 x
⇒
∣
A
∣
2
2
[
x
1
2k
sin¦2kx)

−a
a
=1
k=
nn
2a
( n odd.)⇒sin¦!2ka)=sin¦!nn)=0
⇒RHS=∣ A∣
2
xa⇒Choose A so...∣ A∣
2
=
1
a
A=
1
.
a
2222 Quantum Physics 20067 47
The infinite well and the Uncertainty
Principle
Position uncertainty in well:
Momentum uncertainty in lowest state from classical argument (agrees
with fully quantum mechanical result, as we will see in §4)
Compare with Uncertainty
Principle:
Ground state close to
minimum uncertanty
Ax≃2a
(We know the particle is inside the box.)
State with n = 1 corresponds to a particle bouncing back and forth in the well.
Momentum will be alternately:
!ℏ k or !
ℏn
2a
⇒Momentum uncertainty: A p=2ℏ k=
ℏn
a
=
h
2a
So: Ax A p=2a
h
2a
=h
2222 Quantum Physics 20067 48
3.3 Finite square well
Now make the potential well
more realistic by making the
barriers a finite height V
0
V(x)
x
a
a
V
0
I II
III
Region I: Region II: Region III:
Rae §2.4, B&J §4.6
−
ℏ
2
2m
6
2
m
6 x
2
+V
0
m=Em
Try: m¦ x)=e
\ x
−
ℏ
2
\
2
2m
m+V
0
m=Em
ℏ
2
\
2
2m
=V
0
−E ¯0
\is real.
\=!« «
2
=
2m¦V
0
−E)
ℏ
2
⇒m=C e
« x
+De
−« x
D is not normalisable so decaying
term C is only term allowed. D = 0
−
ℏ
2
2m
6
2
m
6 x
2
=Em
m=Acos¦ kx)+Bsin¦ kx)
k
2
=
2mE
ℏ
2
Free particle solutions apply:
−
ℏ
2
2m
6
2
m
6 x
2
+V
0
m=Em
⇒m=C ' e
« x
+D' e
« x
( «same as in Region 1.)
Decaying term forbidden.
Growing term allowed.
m=D' e
−« x
Assume: 0<E<V
0
2222 Quantum Physics 20067 49
Finite square well (2)
x a ·
Match value and derivative of
wavefunction at region boundaries:
Add and subtract:
x a · +
Match ψ:
Match dψ/dx:
Acos¦ka)−Bsin¦ ka)=Ce
−«a
kAsin¦ka)+kBcos¦ ka)=«Ce
−«a
Acos¦ka)+Bsin¦ ka)=De
−«a
−kAsin¦ ka)+kBcos¦ ka)=−«De
−«a
2Acos¦ka)=¦C+D) e
−«a
2Bsin¦ ka)=¦ D−C) e
−«a
2« Bcos¦ ka)=«¦C−D) e
−«a
2« Asin¦ ka)=«¦C+D) e
−«a
2222 Quantum Physics 20067 50
Finite square well (3)
Divide equations:
Must be satisfied simultaneously:
Cannot be solved algebraically. Convenient form for graphical solution:
k tan¦ ka)=« (Unless A=0andC=−D)
k cot ¦ ka)=−k (Unless B=0andC=D)
Either: k tan¦ ka)=« and B=0 , C=D (Even solution)
Or: k cot ¦ ka)=−« and A=0 , C=−D (Odd solution)
k &« are related by the requirement:
ℏ
2
2m
¦ k
2
+«
2
)=V
0
⇒k
2
+«
2
=k
0
2
Where: k
0
2
=
2mV
0
ℏ
2
Even solution  k tan¦ka)=+
.
¦ k
0
2
−k
2
)
Odd solution  k cot ¦ ka)=−
.
¦ k
0
2
−k
2
)
⇒ Search for intersections of y=k tan¦ ka) or y=k cot ¦ ka) with a circle y=!
.
¦ k
0
2
−k
2
)
2222 Quantum Physics 20067 51
Graphical solution for finite well
5
4
3
2
1
0
1
2
3
4
5
0 5 10
k
ktan(ka)
sqrt(k0^2k^2)
kcot(ka)
sqrt(k0^2k^2)
k
0
=3, a=1
The radius of the circle
corresponds to the
depth of the well.
2222 Quantum Physics 20067 52
Notes
• Penetration of particle into “forbidden” region where V>E
(particle cannot exist here classically)
• Number of bound states depends on depth of potential well,
but there is always at least one (even) state
• Potential is even function, wavefunctions may be even or odd
(we say they have even or odd parity)
•
Limit as V
0
→∞:
k
0
∞, circle becomes very large.
⇒ Solutions at ka=
nn
2
(as for an infinite well.)
2222 Quantum Physics 20067 53
Example: the quantum well
Esaki Kroemer
Quantum well is a “sandwich” made of two different semiconductors in which the energy
of the electrons is different, and whose atomic spacings are so similar that they can be
grown together without an appreciable density of defects:
Electron potential
energy
Position
Now used in many electronic devices (some
transistors, diodes, solidstate lasers)
Material A
(e.g. AlGaAs)
Material B (e.g. GaAs)
2222 Quantum Physics 20067 54
3.4 Particle Flux
In order to analyse problems involving
scattering of free particles, need to understand
normalization of freeparticle planewave
solutions.
This problem is related to Uncertainty Principle:
Momentum is completely defined
Position completely undefined;
single particle can be anywhere
from ∞ to ∞, so probability of
finding it in any finite region is
zero
Conclude that if we try to
normalize so that
will get A=0.
Rae §9.1; B&M
§5.2, B&J §3.2
∫
−∞
∞
∣Ae
i ¦k x −ot )
∣
2
dx=
∫
−∞
∞
∣A∣
2
dx=∞
∫
−∞
∞
∣1∣
2
dx=1
2222 Quantum Physics 20067 55
Particle Flux (2)
More generally: what is rate of change of
probability that a particle exists in some region
(say, between x=a and x=b)?
x
a b
Use timedependent Schrődinger equation:
6
6t
∫
a
b
1
∗
1dx=
∫
a
b
[
1
∗
61
6t
+1
61
∗
6t

dx
i ℏ
61
6t
=
[
−
ℏ
2
2m
6
2
6 x
2
+V

1 ; i ℏ
61
∗
6t
=
[
−
ℏ
2
2m
6
2
6 x
2
+V

1
∗
⇒
∫
a
b
¦
1
i ℏ
1
∗
[
−
ℏ
2
2m
6
2
6 x
2
+V

1−
1
i ℏ
1
[
−
ℏ
2
2m
6
2
6 x
2
+V

1
∗
¦
dx
=
1
i ℏ
−
ℏ
2
2m
∫
a
b
[
1
∗
6
2
1
6 x
2
−1
6
2
1
∗
6 x
2

dx
=
i ℏ
2m
∫
a
b
[
1
∗
6
2
1
6 x
2
−1
6
2
1
∗
6 x
2

dx
2222 Quantum Physics 20067 56
Particle Flux (3)
Integrate by parts:
x
a b
Interpretation:
Flux entering
at x=a
Flux leaving
at x=b
Note: a wavefunction that is
real carries no current
Note: for a stationary state can use either ψ(x) or Ψ(x,t)
d
dt
∫
a
b
1
∗
1dx=
i ℏ
2m
[
1
∗
d 1
dx
−1
d1
∗
dx

a
b
−
i ℏ
2m
∫
a
b
¦
d1
∗
dx
d 1
dx
−
d 1
dx
d 1
∗
dx
¦
dx
=
i ℏ
2m
¦
1
∗
d 1
dx
−1
d 1
∗
dx
)
∣
∣
x=b
−
i ℏ
2m
¦
1
∗
d 1
dx
−1
d 1
∗
dx
)
∣
∣
x=a
Flow of probability leaving at x = b Flow of probability entering at x = a
Particle flux at position x :
I¦ x)=−
i ℏ
2m
[
1
∗
61
6 x
−1
61
∗
6 x

or I¦ x)=
ℏ
m
Im
[
1
∗
61
6 x

2222 Quantum Physics 20067 57
Particle Flux (4)
Sanity check: apply to freeparticle
plane wave.
# particles passing x per unit time = # particles per unit length × velocity
Makes sense:
Wavefunction describes a “beam” of particles.
1¦ x , t )=Ae
i ¦k x−ot )
; 1
∗
=A
∗
e
−i ¦ k x−ot )
61
6 x
=ikAe
i ¦ k x−ot )
;
61
∗
6 x
=−ikA
∗
e
−i ¦k x−ot )
⇒ Flux I¦ x)=−
i ℏ
2m
[ ¦ A
∗
e
−i ¦k x−ot )
)¦ikAe
i ¦k x−ot )
)−¦ Ae
i ¦ k x−ot )
)¦−ikA
∗
e
−i ¦ k x−ot )
)
=−
i ℏ
2m
[ 2ikAA
∗
=−
i ℏ
2m
[ 2ik∣A∣
2

=
∣A∣
2
ℏ k
m
Two common normalising methods:
1) One particle per unit length.
2)One particle per unit time.
⇒∣A∣
2
=1
⇒
∣A∣
2
ℏk
m
=1
We will use this method.
2222 Quantum Physics 20067 58
3.5 Potential Step
Consider a potential which rises suddenly
at x=0:
x
V(x)
0
V
0
Case 1: E<V
0
(below step)
x<0 x>0
Boundary condition: particles only
incident from left
Rae §9.1; B&J §4.3
Case 1
(But E > 0 )
Free particle S.E.:
−
ℏ
2
2m
6
2
m
6 x
2
=Em
⇒m=Ae
ikx
+Be
−ikx
With:
ℏ
2
k
2
2m
=E
Choose 1 particle per unit length
in incoming beam⇒A=1
Same as
region 2 of
finite well.
−
ℏ
2
2m
6
2
m
6 x
2
+V
0
m=Em
⇒m=Ce
« x
+De
−« x
With:
ℏ
2
«
2
2m
=V
0
−E
The Ce
«x
term is not normalisable.
Regions 1 & 3
of finite well.
2222 Quantum Physics 20067 59
Potential Step (2)
Continuity of ψ at x=0:
d
Continuity of at 0:
d
x
x
v
·
Solve for reflection and transmission:
1+B=D
i k ¦1−B)=−« D
¦i k× equation 1 )+ equation 2:
2i k=¦i k−«) D ⇒ D=
2i k
¦i k−«)
¦«× equation 1 )+ equation 2:
¦«+i k )+¦«−i k ) B=0 ⇒ B=−
¦«+i k )
¦«−i k )
2222 Quantum Physics 20067 60
Transmission and reflection coefficients
Incident particle flux from left=
ℏk
m
What is the flux reflected back to the left? :
−
i ℏ
2m
[
1
∗
61
6 x
−1
61
∗
6 x

¦m=Be
−i k x
)
=−
i ℏ
2m
∣
B
∣
2
[ e
i k x
¦−i k e
−i k x
)−e
i k x
¦i k e
i k x
)
=−
ℏ k
m
∣
B
∣
2
Hence the probability of reflection:
R=
Reflected flux
Incident flux
=∣B∣
2
=BB
∗
=
«+i k
«−i k
«−i k
«+i k
=1
So all particles are reflected.
Transmitted flux: ¦m=De
−«x
)
−
i ℏ
2m
∣
D
∣
2
[ e
−« x
¦−«e
−« x
)−e
−« x
¦−«e
−« x
)
=0
i.e.: Probability of transmission T=0
2222 Quantum Physics 20067 61
Potential Step (3)
Case 2: E>V
0
(above step)
Solution for x>0 is now
Matching conditions:
Transmission and reflection coefficients:
m¦ x)=F e
i k ' x
+G e
−i k ' x
With:
ℏ
2
k
2
2 m
=E−V
0
No incoming particles from right ⇒ G=0
m continuous. ¦1+B)=F
6m
6 x
continuous. i k ¦1−B)=i k ' F
¦i k× equation 1)+equation 2 ⇒ 2i k=i ¦ k+k ' ) F ⇒ B=
k−k '
k+k '
¦i k ' × equation 1)+equation 2 ⇒ i ¦ k ' −k )+i ¦k ' +k ) B=0 ⇒ B=
k−k '
k+k '
By our argument, reflection probability:
R=∣B∣
2
=
¦ k−k ' )
2
¦ k+k ' )
2
 No longer 1 if k=k '
2222 Quantum Physics 20067 62
Summary of transmission through potential
step
Notes:
•Some penetration of particles into forbidden region even for energies
below step height (case 1, E<V
0
);
•
No transmitted particle flux, 100% reflection (case 1, E<V
0
);
•Reflection probability does not fall to zero for energies above barrier (case
2, E>V
0
).
•Contrast classical expectations:
100% reflection for E<V
0
, with no penetration into barrier;
100% transmission for E>V
0
Transmitted flux: =∣F∣
2
ℏ k '
m
=
ℏ k '
m
4k
2
¦ k+k ' )
2
 Transmission probability: =
Transmitted flux
Incident flux
=
4 k k '
¦ k+k ' )
2
2222 Quantum Physics 20067 63
Summary of transmission through potential
step (Cont.)
Check R+T=
¦ k−k ' )
2
¦ k+k ' )
2
+
4k k '
¦ k+k ' )
2
=
k
2
−2k k ' +k '
2
+4 k k '
¦ k+k ' )
2
=1 as required.
2222 Quantum Physics 20067 64
3.6 Rectangular Potential Barrier
Rae §2.5; B&J §4.4; B&M §5.9
Now consider a potential barrier of
finite thickness:
V(x)
x
a
I II
III
0
V
0
Boundary condition: particles only
incident from left
Region I: Region II: Region III:
Assume 0<E<V
0
m¦ x)=Ae
i k x
+Be
−i k x
¦
With
ℏ
2
k
2
2m
=E
)
Take A=1 (i.e. 1 particle per
unit length.)
m=C e
« x
+De
−« x
¦
With
ℏ
2
«
2
2m
=V
0
−E
)
N.B: No reason to exclude either
solution since region II is finite.
m¦ x)=F e
i k x
+Ge
−i k x
(With k as in region I.)
Exclude G term as this term
represents particles travelling
from the right.
⇒ G=0
2222 Quantum Physics 20067 65
Rectangular Barrier (2)
0 x ·
Match value and derivative of
wavefunction at region boundaries:
x a · +
Match ψ:
Match dψ/dx:
Eliminate wavefunction in central
region:
1+B=C+D [1
i k ¦1−B)=«¦C−D) [ 3
Ce
«a
+De
−«a
=F e
i k a
[ 2
«¦C e
«a
−De
−«a
)=i k F e
i k a
[ 4
Eliminate B:
i k [1+[3 : 2i k=¦i k+«)C+¦i k−«) D
«[ 2+[ 4 : 2«C e
«a
=¦«+i k ) F e
i k a
«[ 2−[ 4 : 2« De
−«a
=¦«−i k ) F e
i k a
Eliminate C & Din the same way...
To get F=
4i k «e
−i k a
¦«+i k )
2
e
−«a
−¦«−i k )
2
e
«a
2222 Quantum Physics 20067 66
Rectangular Barrier (3)
Transmission and reflection coefficients:
For very thick or high barrier:
Nonzero transmission (“tunnelling”) through classically
forbidden barrier region:
Transmission probability: T=
∣F∣
2
∣A∣
2
=
∣F∣
2
1
=
16 k
2
«
2
∣¦«+i k )
2
e
−«a
−¦«−i k )
2
e
«a
∣
2
Reflection probability: R=∣B∣
2
=1−T
T≃
16 k
2
«
2
∣¦«−i k )
2
∣
2
e
2« a
=
16 k
2
«
2
¦«−i k)
2
e
−2«a
=
16 E¦V
0
−E)
V
0
2
e
−«a
«a≫1 ⇒ e
«a
≫e
−«a
67
Examples of tunnelling
Tunnelling occurs in many situations in physics and astronomy:
1. Nuclear fusion (in stars
and fusion reactors)
3. Field emission of
electrons from surfaces
(e.g. in plasma displays)
V
2
0 nucleus
( )
Barrier height ~ ~ MeV
4
thermal energies (~keV)
Ze
r rr
?
Internuclear
distance x
Coulomb
interaction
(repulsive)
Strong nuclear
force
(attractive)
Incident
particles
2. Alphadecay
Distance x of α
particle from nucleus
V
Initial αparticle
energy
Distance x of
electron from
surface
V
Work function
W
Vacuum
Material
2222 Quantum Physics 20067 68
3.7 Simple Harmonic Oscillator
0
2 2 2
0
Force
Angular frequency =
1 1
Potential energy ( )
2 2
F kx
k
m
V x kx m x
u
u
·
· ·
Example: particle on a
spring, Hooke’s law
restoring force with spring
constant k:
Mass m
x
Timeindependent
Schrődinger equation:
Problem: still a linear differential equation
but coefficients are not constant.
Simplify: change variable to
Rae §2.6; B&M §5.5; B&J §4.7
−
ℏ
2
2m
d
2
m
d x
2
+
1
2
mo
0
x
2
m=Em
y=
¦
mo
0
ℏ
)
1
2
x ⇒
d
d y
=
d x
d y
d
d x
=
¦
ℏ
mo
0
)
−
1
2 d
d x
Substitute: −
ℏ
2m
mo
0
ℏ
d
2
m
d y
2
+
1
2
ℏo
0
y
2
m=E y
⇒
d
2
m
d y
2
+¦o−y
0
)m=0 o=
2 E
ℏ o
0
2222 Quantum Physics 20067 69
Simple Harmonic Oscillator (2)
Asymptotic solution in the
limit of very large y:
Check:
m¦ y)=y
n
exp
¦
!
y
2
2
)
d m
d y
=n y
¦ n−1)
exp
¦
!
y
2
2
)
!y
¦n+1)
exp
¦
!
y
2
2
)
⇒
d
2
m
d y
2
=[ n¦n−1) y
¦n−2)
!¦2n−1) y
n
+y
¦ n+2)
 exp
¦
!
y
2
2
)
≃y
¦n+2)
exp
¦
!
y
2
2
)
=y
2
m (For large y .)
Substitute: m¦ y)=H¦ y) exp
¦
!
y
2
2
)
¦
S.E. for large y
d
2
m
d y
2
−y
2
m=0
is satisfied.
Only ve part gives
normalisable solution.
)
2222 Quantum Physics 20067 70
Simple Harmonic Oscillator (2) (Cont.)
Substitute in S.E:
[ H ' ' ¦ y)−2 y H ' ¦ y)+¦ y
2
−1) H¦ y) exp
¦
−
y
2
2
)
+ ¦o−y
2
) H¦ y)exp
¦
−
y
2
2
)
= 0
⇒ H ' ' ¦ y)−2 y H ' ¦ y)+¦o−1) H¦ y)=0
Equation for H:
d m
d y
=[ H ' ¦ y)−y H¦ y) exp
¦
−
y
2
2
)
d
2
m
d y
2
[ H ' ' ¦ y)−2 y H ' ¦ y)−H¦ y)+y
2
H ¦ y) exp
¦
−
y
2
2
)
H is the correction function to find all solutions.
2222 Quantum Physics 20067 71
Simple Harmonic Oscillator (3)
Must solve this ODE by the powerseries
method (Frobenius method); this is done as
an example in 2246.
We find:
•The series for H(y) must terminate in order to obtain a normalisable solution
•Can make this happen after n terms for either even or odd terms in series (but not both)
by choosing:
Label resulting functions of H by
the values of n that we choose.
H
n
is known as the nth Hermite
polynomial.
H ¦ y)=
∑
p=0
∞
a
p
y
p
o=2n+1 (For some integer n.) ⇒ E=ℏo
0
¦
n+
1
2
)
If n is even, we must also choose a
1
=0, so all odd terms in the series vanish giving an even solution.
If n is odd, we must also chose a
0
=0, so all even terms vanish to give an odd solution.
2222 Quantum Physics 20067 72
The Hermite polynomials
For reference, first few Hermite polynomials are:
( )
( )
( )
( )
( )
0
1
2
2
3
3
4 2
4
1;
2 ;
4 2;
8 12 ;
16 48 12.
H y
H y y
H y y
H y y y
H y y y
·
·
·
·
· +
NOTE:
H
n
contains y
n
as the highest power.
Each H is either an odd or an even function, according to whether n
is even or odd.
2222 Quantum Physics 20067 73
Simple Harmonic Oscillator (4)
Transforming back to the original variable x, the
wavefunction becomes:
Probability per unit length of finding the particle is:
m
0
¦ x)=C
0
exp
¦
−mo
0
x
2
2ℏ
)
, m
1
¦ x)=C
1
x exp
¦
−mo
0
x
2
ℏ
)
, etc.
C
0
, C
1
, etc. are normalising constants that satisfy:
∫
∣m
n
¦ x)∣
2
d x=1
∣
C m
n
¦ x)
∣
2
when the system is in state n.
E.g.:
∣
Cm
0
¦ x)
∣
2
=
∣
C
0
∣
2
exp
¦
−mo
0
x
2
ℏ
)
2222 Quantum Physics 20067 74
Simple Harmonic Oscillator (4) (Cont.)
Compare classical result: probability of finding particle in a length δx is proportional to
the time δt spent in that region:
For a classical particle with total energy E, velocity is given by
p
classical
¦ x) d x o d t o
d x
v
1
2
mv
2
+V ¦ x)=E ⇒ V =
.
2¦ E−V ¦ x))
m
⇒ p
classical
o
1
.
E−V ¦ x)
=
1
.
E−
1
2
mo
0
x
2
2222 Quantum Physics 20067 75
Notes
• “Zeropoint energy”:
• “Quanta” of energy:
• Even and odd solutions
• Applies to any simple harmonic oscillator, including
– Molecular vibrations
– Vibrations in a solid (hence phonons)
– Electromagnetic field modes (hence photons), even though this field does not
obey exactly the same Schrődinger equation
• You will do another, more elegant, solution method (no series or
Hermite polynomials!) next year
• For highenergy states, probability density peaks at classical turning
points (correspondence principle)
E=
¦
n+
1
2
)
ℏo
0
in n
th
state.
Ground state energy: E
0
= 1/ 2 ℏ o
0
Can only add or subtract multiples of ℏo
0
2222 Quantum Physics 20067 76
4 Postulates of QM
This section puts quantum mechanics onto a more formal mathematical
footing by specifying those postulates of the theory which cannot be
derived from classical physics.
Main ingredients:
3. The wave function (to represent the state of the system);
4. Hermitian operators (to represent observable quantities);
5. A recipe for identifying the operator associated with a given
observable;
6. A description of the measurement process, and for predicting the
distribution of outcomes of a measurement;
7. A prescription for evolving the wavefunction in time (the time
dependent Schrődinger equation)
2222 Quantum Physics 20067 77
4.1 The wave function
Postulate 4.1: There exists a wavefunction Ψ that is a continuous,
squareintegrable, singlevalued function of the coordinates of all the
particles and of time, and from which all possible predictions about the
physical properties of the system can be obtained.
Examples of the meaning of “The coordinates of all the particles”:
For a single particle moving in
one dimension:
For a single particle moving in
three dimensions:
For two particles moving in three
dimensions:
The modulus squared of Ψ for any value of the coordinates is the probability
density (per unit length, or volume) that the system is found with that particular
coordinate value (Born interpretation).
x
¦ x , y , z) ¦ r , 0, !) etc.
¦ x
1
, y
1
, z
1
, x
2
, y
2
, z
2
) etc.
2222 Quantum Physics 20067 78
4.2 Observables and operators
1
2
3
4
ˆ
[ ] 2
ˆ
[ ]
ˆ
[ ]
d
ˆ
[ ]
d
L f f
L f xf
L f f
f
L f
x
+
Postulate 4.2.1: to each observable quantity is associated a linear, Hermitian
operator (LHO).
Examples: which of the operators
defined by the following equations are
linear?
Note: the operators
involved may or may
not be differential
operators (i.e. may or
may not involve
differentiating the
wavefunction).
An operator
´
L is linear if, and only if:
´
L[ c
1
f
1
+c
2
f
2
=c
1
´
L[ f
1
+c
2
´
L[ f
2

¦
For arbitrary functions f
1
& f
2
and constants c
1
& c
2
.
)
NOT linear as
´
L
1
[ c
1
f
1
+c
2
f
2
=c
1
f
1
+c
2
f
2
+2
Linear as
´
L
2
[ c
1
f
1
+c
2
f
2
=c
1
x f
1
+c
2
x f
2
NOT linear as
´
L
3
[c
1
f
1
+c
2
f
2
=
.
c
1
f
1
+c
2
f
2
Linear as
´
L
4
[ c
1
f
1
+c
2
f
2
=c
1
d f
1
d x
+c
2
d f
2
d x
2222 Quantum Physics 20067 79
Hermitian operators
ij
M
An operator O is Hermitian if and only if:
for all functions f,g vanishing at infinity.
Compare the definition of a Hermitian matrix M:
Analogous if we identify a matrix element with an integral:
(see 3226 course for more
detail…)
∫
−∞
∞
f
∗
¦
´
O g) dx=
[
∫
−∞
∞
g
∗
¦
´
O f ) dx

∗
M
i j
=
[
M
j i

∗
∫
−∞
∞
f
i
∗
¦
´
O f
j
) dx
2222 Quantum Physics 20067 80
Hermitian operators: examples
The operator is Hermitian x
d
The operator is not Hermitian.
dx
2
2
d
The operator is Hermitian.
dx
∫
−∞
∞
f
∗
¦ x g) dx=
∫
−∞
∞
g x f
∗
dx=
[
∫
−∞
∞
g
∗
x f dx

∗
(Since x is real.)
∫
−∞
∞
f
∗
dg
dx
dx=[ f
∗
g 
−∞
∞
−
∫
−∞
∞
g
df
∗
dx
dx [ f
∗
g=0 as f & g vanish at ∞
=−
[
∫
−∞
∞
g
∗
df
dx
dx

∗
∴ Not Hermitian because of ve sign. (This is 'AntiHermitian.')
∫
−∞
∞
f
∗
d
2
g
dx
2
dx=
[
f
∗
dg
dx

−∞
∞
−
∫
−∞
∞
dg
dx
df
∗
dx
dx
=−
[
df
∗
dx
g

−∞
∞
+
∫
−∞
∞
d
2
f
∗
dx
2
g dx=
∫
−∞
∞
g
∗
d
2
f
dx
2
dx
2222 Quantum Physics 20067 81
Eigenvectors and eigenfunctions
Postulate 4.2.2: the eigenvalues of the operator represent the possible
results of carrying out a measurement of the corresponding quantity.
Definition of an eigenvalue for a general linear operator:
Example: the timeindependent Schrődinger
equation:
Compare definition of an eigenvalue of a matrix:
´
Q!
n
=q
n
!
n
!
n
is an eigenfunction.
q
n
is an eigenvalue.
M v=\
n
v
n
v
n
is an eigenvector.
\
n
is an eigenvalue.
´
H m=Em
The energy in the T.I.S.E. is an eigenvalue of the Hamiltonian operator, and m is an eigenfunction.
Interpretation of Eigenfunction: It is a state of the system in which there is a definite value
of the quantity concerned.
2222 Quantum Physics 20067 82
Postulate 4.2.3: immediately after making a measurement, the wavefunction
is identical to an eigenfunction of the operator corresponding to the
eigenvalue just obtained as the measurement result.
Proof:
Ensures that we get the same result if we immediately remeasure the
same quantity.
Important fact: The eigenvalues of a Hermitian operator are real (like the
eigenvalues of a Hermitian matrix).
Let
´
Q!
m
=q
m
!
m
(Where
´
Q is Hermitian.)
Then
[
∫
−∞
∞
!
m
∗
¦
´
Q!
m
) dx

=
[
∫
−∞
∞
!
m
∗
¦
´
Q!
m
) dx

∗
(Using f =g=!
m
)
⇒
[
∫
−∞
∞
!
m
∗
¦
´
Q!
m
) dx

=q
m
∫
−∞
∞
∣!
m
∣
2
dx (Which is real.)
But
∫
−∞
∞
∣
!
m
∣
2
dx is real. ∴ q
m
is real.
Start with wavefunction 1 and then measure quantity
´
Q ⇒ Obtain result q
m
( one of the
eigenvalues of
´
Q ) ⇒ Leave system with corresponding wavefunction !
m
2222 Quantum Physics 20067 83
4.3 Identifying the operators
Postulate 4.3: the operators representing the position and
momentum of a particle are
Other operators may be obtained from the corresponding
classical quantities by making these replacements.
Examples:
The Hamiltonian (representing the total energy as a
function of the coordinates and momenta)
Angular momentum:
(one dimension)
(three dimensions)
´ x=x
i.e. ´ x m=x m
´ p
x
=−i ℏ
6
6 x
i.e. ´ p
x
m=−i ℏ
d m
dx
´ r=r ´p=−i ℏ
[
i
6
6 x
+ j
6
6 y
+k
6
6 z

=−i ℏ ∇
´
H=
´
p
2
2m
+V ¦ ´ r )=
−ℏ
2
2m
∇
2
+V ¦ ´ r) or
−ℏ
2
2m
6
2
6 x
2
+V ¦ x)
´
L=´ r×´p=−i ℏ r×∇ ⇒
´
L!=−i ℏ r×¦ ∇m)
2222 Quantum Physics 20067 84
Eigenfunctions of momentum
The momentum operator is Hermitian, as
required:
Its eigenfunctions are plane waves:
∫
−∞
∞
f
∗
¦ ´p g) dx=
[
−i ℏ
∫
−∞
∞
f
∗
¦
dg
dx
)
dx

=−i ℏ
[
−
∫
−∞
∞
g
∗
¦
df
dx
)
dx

∗
=
[
−i ℏ
∫
−∞
∞
g
∗
df
dx
dx

∗
=
[
∫
−∞
∞
g
∗
¦ ´p f ) dx

∗
¦
Factor of −i makes ´ p
Hermitian, even though
6
6 x
isn't.
)
´ p
x
e
i k x
=−i ℏ
de
i k x
dx
=−i ℏ i k e
i k x
=ℏ k e
i k x
e
i k x
is indeed an eigenfunction of ´ p
x
with eigenvalue ℏk
This corresponds to a state having a definite momentum ℏ k (in agreement with DeBroglie.)
2222 Quantum Physics 20067 85
Orthogonality of eigenfunctions
The eigenfunctions of a Hermitian operator belonging to
different eigenvalues are orthogonal.
Proof:
If
´
Q!
n
=q
n
!
n
;
´
Q!
m
=q
m
!
m
with q
n
≠q
m
then
∫
−∞
∞
!
n
∗
!
m
dx=0
Use Hermitian definition, taking : f =!
n
, g=!
m
⇒
∫
−∞
∞
!
n
∗
¦
´
Q!
m
) dx=
[
∫
−∞
∞
!
m
∗
¦
´
Q!
n
) dx

∗
RHS=
[
q
n
∫
−∞
∞
!
m
∗
!
n
dx

∗
=q
n
∫
−∞
∞
!
m
!
n
∗
dx (Since q
n
is real.)
LHS=q
m
∫
−∞
∞
!
n
∗
!
m
dx
We chose q
m
≠q
n
⇒
∫
−∞
∞
!
n
∗
!
m
dx=0
RHS=LHS=¦q
m
−q
n
)
∫
−∞
∞
!
n
∗
!
m
dx=0
2222 Quantum Physics 20067 86
Orthonormality of eigenfunctions
What if two eigenfunctions have the same eigenvalue? (In this
case the eigenvalue is said to be degenerate.)
Any linear combination of these eigenfunctions is also an
eigenfunction with the same eigenvalue:
So we are free to choose as the eigenfunctions two linear
combinations that are orthogonal.
If the eigenfunctions are all orthogonal and normalized,
they are said to be orthonormal.
´
Q¦ c
1
!
1
+c
2
!
2
)=c
1
´
Q!
1
+c
2
´
Q!
2
=c
1
q!
1
+c
2
q!
2
=q¦c
1
!
1
+c
2
!
2
)
¦
´
Q
1
!
1
=q!
1
´
Q
2
!
2
=q!
2
)
We can choose to have all the eigenfunctions orthogonal regardless of
whether the eigenvalues are the same or different.
∫
−∞
∞
!
n
∗
!
m
dx=6
nm
2222 Quantum Physics 20067 87
Orthonormality of eigenfunctions: example
Consider the solutions of the timeindependent Schrődinger equation
(energy eigenfunctions) for an infinite square well:
We chose the constants so that normalization is correct:
¦ Eigenfunctions of
´
H)
!
n
=
¦
1
.
a
cos
¦
nnx
2a
)
, for odd n
1
.
a
sin
¦
nn x
2a
)
, for even n¦
For −a<x<a, otherwise 0
∫
−a
a
∣
!
n
∣
2
dx=1
Consider 2 different values n , m:
[1] 2 odd values:
∫
−a
a
!
n
∗
!
m
dx=
∫
−a
a
1
a
cos
¦
nn x
2a
)
cos
¦
mnx
2a
)
dx
=
1
2a
∫
−a
a
[
cos
¦
¦ n+m)n x
2a
)
+cos
¦
¦ n−m)nx
2a
)

dx
=
1
2a
[
2a
¦ n+m)n
sin
¦
¦n+m) nx
2a
)
2a
¦n−m) n
sin
¦
¦ n−m)nx
2a
)

−a
a
=0
cos ocos ß=
1
2
[ cos ¦o−ß)+cos¦o+ß)
2222 Quantum Physics 20067 88
Orthonormality of eigenfunctions: example
(Cont.)
[2] 2 even values:
Similarly =0 sin osin ß=
1
2
[
cos ¦o−ß)−cos ¦o+ß)

[3] Even & odd values:
∫
−a
a
!
n
∗
!
m
dx=0 by symmetry.
⇒
∫
−a
a
!
n
∗
!
m
dx=6
nm
2222 Quantum Physics 20067 89
Complete sets of functions
The eigenfunctions φ
n
of a Hermitian operator
form a complete set, meaning that any other
function satisfying the same boundary conditions
can be expanded as
If the eigenfunctions are chosen to be orthonormal, the
coefficients a
n
can be determined as follows:
We will see the significance of such expansions when we
come to look at the measurement process.
m¦ x)=
∑
n
a
n
!
n
¦ x)
Where: mis an arbitrary function,
a
n
are numbers, and !
n
are eigenfunctions.
Consider:
∫
−∞
∞
!
m
∗
mdx=
∑
n
a
n
∫
−∞
∞
!
m
∗
!
n
dx
=
∑
n
a
n
6
mn
=a
m
⇒ Find number a
m
, multiply m by !
m
∗
and integrate.
2222 Quantum Physics 20067 90
Normalization and expansions in complete
sets
The condition for normalizing the wavefunction is now
If the eigenfunctions φ
n
are orthonormal, this becomes
Natural interpretation: the probability of finding the system in the state
φ
n
(x) (as opposed to any of the other eigenfunctions) is
2
n
a
1=
∫
−∞
∞
∣m¦ x)∣
2
dx=
∫
−∞
∞
[
∑
m
a
m
!
m
¦ x)

∗
[
∑
n
a
n
!
n
¦ X )

dx=
∑
m
∑
n
a
m
∗
a
n
∫
−∞
∞
!
m
∗
¦ x)!
n
∗
¦ x) dx
∫
−∞
∞
!
m
∗
¦ x) !
n
∗
¦ x) dx=6
mn
=
¦
1 m=n
0 otherwise
¦
1=
∑
m
∑
n
a
m
∗
a
n
6
mn
=
∑
n
∣a
n
∣
2
2222 Quantum Physics 20067 91
Expansion in complete sets: example
Consider an infinite square well, with a particle confined to −a<x<a
Hamiltonian has eigenfunctions:
m
n
¦ x)=
¦
¦
1
.a
cos¦
nnx
2a
) ( n odd)
1
.
a
sin¦
nnx
2a
) ( n even)¦
For −a<x<a
0 otherwise
¦
So any function f ¦ x) satisfying some boundary conditions
(i.e zero outside well) can be represented as:
f ¦ x)=
∑
n odd
a
n
1
.
a
cos¦
nnx
2a
)+
∑
n even
1
.
a
sin¦
nnx
2a
)
Eigenfunctions are orthonormal (see previous working)
⇒ a
n
=
¦
∫
−a
a
1
.
a
cos¦
nnx
2a
) f ¦ x) dx ( n odd)
∫
−a
a
1
.a
sin¦
nnx
2a
) f ¦ x) dx ( n even)¦
This is a Fourier series representation of f ¦ x)
2222 Quantum Physics 20067 92
4.4 Eigenfunctions and measurement
Postulate 4.4: suppose a measurement of the quantity Q is made, and that
the (normalized) wavefunction can be expanded in terms of the
(normalized) eigenfunctions φ
n
of the corresponding operator as
Then the probability of obtaining the corresponding eigenvalue q
n
as the
measurement result is
2
n
a
What is the meaning of these “probabilities” in
discussing the properties of a single system?
Still a matter for debate, but usual interpretation is that
the probability of a particular result determines the
frequency of occurrence of that result in measurements
on an ensemble of similar systems.
Corollary: if a system is definitely in eigenstate φ
n
, the result measuring
Q is definitely the corresponding eigenvalue q
n
.
m¦ x)=∑
n
a
n
!
n
¦ x)
2222 Quantum Physics 20067 93
Commutators
In general operators do not commute: that is to say, the order in
which we allow operators to act on functions matters:
For example, for position and momentum operators:
We define the commutator as the
difference between the two orderings:
Two operators commute if, and only if, their
commutator is zero. Note: The commutator
of any operator with itself is zero!
´
Q
´
Rm≠
´
R
´
Qm (In general)
(In x direction)
´ x¦ ´pm)=x X−i ℏ
d m
d x
⇒ ´ x ´pm−´p ´xm=i ℏ m
´p¦ ´ xm)=−i ℏ
6
6 x
¦ x m)=−i ℏ
¦
m+x
d m
d x
)
⇒ [ ´ x , ´ p=´ x ´p−´p ´ x=i ℏ
[
´
Q ,
´
R=
´
Q
´
R−
´
R
´
Q
[
´
Q,
´
Q=
´
Q
´
Q−
´
Q
´
Q=0
So, for position and momentum:
[
´ x , ´ p
x

=i ℏ
But:
[
´x , ´ p
y

=0=
[
´ x , ´ p
z

2222 Quantum Physics 20067 94
Compatible operators
Two observables are compatible if their operators share the same
eigenfunctions (but not necessarily the same eigenvalues).
Consequence: two compatible observables can have preciselydefined
values simultaneously.
Compatible operators commute with one another:
Measure
observable Q,
obtain result q
m
(an eigenvalue of
Q)
Wavefunction of
system is
corresponding
eigenfunction φ
m
Measure observable R,
definitely obtain result
r
m
(the corresponding
eigenvalue of R)
Wavefunction of
system is still
corresponding
eigenfunction φ
m
Remeasure Q,
definitely
obtain result q
m
once again
Can also show the converse: any two
commuting operators are compatible.
Expansion in terms of
joint eigenfunctions of
both operators
Consider a general wavefunction m¦ x)=∑
n
a
n
!
n
¦ x)
´
Q
¦
´
Rm
)
=
´
Q
[
∑
n
a
n
r
n
!
n
¦ x)

( r
n
eigenvalues of
´
R)
=∑
n
a
n
q
n
r
n
!
n
¦ x) ( Using linearity of operator)
And:
´
R
¦
´
Qm
)
=∑
n
a
n
r
n
q
n
!
n
¦ x) ⇒
´
Q
´
Rm=
´
R
´
Qm for any m
⇒ [
´
Q,
´
R=0
Uncertainty of measurement is proportional to commutator.
Commuator here is zero, so no uncertainty.
2222 Quantum Physics 20067 95
Example: measurement of position
Eigenfunctions of position operator
´
x would have to be states of definite position.
'Dirac 6 functions'.
For now, consider approximate eigenstates: Suppose we have a series of detectors (in one dimension)
each sensitive to the presence of a particle in length A
Detectors are n , n+1, n+2 etc. Starting at x
n
, x
n+1
etc. on the x axis.
Corresponding eigenfunctions: !
n
¦ x)=
¦
A
−
1
2
when x in n
th
region
0 otherwise
¦
Check normalisation: ∫
−∞
∞
∣
!
n
∣
2
dx= ∫
x
n
x
n
+A
1
A
dx=A
1
A
=1
Check orthogonality: ∫
−∞
∞
!
n
∗
!
m
dx=0 (If n≠m)
Since at least one of !
n
and !
m
is always zero.
!
n
¦ x)
x
n
x
n+1
A
−
1
2
2222 Quantum Physics 20067 96
Example: measurement of position (2)
Now take system with general wavefunction as m¦ x)=∑
n
a
n
!
n
¦ x) (Becomes extinct as A0)
Where: a
n
=∫
−∞
∞
!
n
∗
¦ x) m¦ x) dx=
¦
∫
−∞
∞
m¦ x) dx
)
A
−
1
2
≃A
−
1
2
m¦ x
n
)
Probability that n
th
detector 'fires' =
∣
a
n
∣
2
=A∣m¦ x
n
)∣
2
⇒ Consistent with Born interpretation that ∣m∣
2
is a probability density. (Probability per unit length.)
Schematically:
x x
≃
Measure position
x
`
n
th
detector fires.
2222 Quantum Physics 20067 97
Expectation values
The average (mean) value of measurements of the quantity Q is therefore the sum of
the possible measurement results times the corresponding probabilities:
We can also write this as:
〈 Q〉=
∑
n
∣
a
n
∣
2
q
n
∫
−∞
∞
m
∗
¦ x)
¦
´
Qm¦ x)
)
dx =
∫
−∞
∞
¦
∑
n
a
n
!
n
¦ x)
)
∗
¦
∑
m
a
m
´
Q!
m
¦ x)
)
dx
=
∑
n
∑
m
q
m
a
n
∗
a
m
∫
−∞
∞
!
n
∗
!
m
dx Since
´
Q!
m
=q
m
!
m
¦
∫
−∞
∞
!
n
∗
!
m
dx=6
mn
)
=
∑
n
q
n
∣a
n
∣
2
= 〈
´
Q〉
2222 Quantum Physics 20067 98
4.5 Evolution of the system
Postulate 4.5: Between measurements (i.e. when it is not disturbed by
external influences) the wavefunction evolves with time according to the
timedependent Schrődinger equation.
This is a linear, homogeneous differential equation, so the linear combination of any two
solutions is also a solution: the superposition principle.
i ℏ
61
6t
=
´
H 1 Where
´
H is the Hamiltonian operator.
i ℏ
61
1
6t
=
´
H 1
1
i ℏ
61
2
6t
=
´
H 1
2
⇒ i ℏ
6
6t
¦
c
1
1
1
+c
2
1
2
)
=c
1
´
H 1
1
+c
2
´
H 1
2
=
´
H
¦
c
1
1
1
+c
2
1
2
)
(Since
´
H is linear.)
2222 Quantum Physics 20067 99
Calculating time dependence using expansion
in energy eigenfunctions
Suppose the Hamiltonian is timeindependent. In that case we know that solutions of the
timedependent Schrődinger equation exist in the form:
where the wavefunctions ψ(x) and the energy E correspond to one solution of
the timeindependent Schrődinger equation:
We know that all the functions ψ
n
together form a complete set, so we can expand
Hence we can find the complete time dependence
(superposition principle):
1
n
¦ x , t )=exp
¦
−
i E
n
t
ℏ
)
m
n
¦ x)
´
H m
n
=E
n
m
n
1¦ x , 0)=∑
n
a
n
m
n
¦ x)
1¦ x , t )=∑
n
a
n
1¦ x , t )=∑
n
a
n
e
¦
−
i E
n
t
ℏ
)
m
n
¦ x)
2222 Quantum Physics 20067 100
Timedependent behaviour: example
Suppose the state of a particle in an infinite square well at time t=0
is a `superposition’ of the n=1 and n=2 states
Wave function at a subsequent time t
Probability density
1¦ x , 0)=c
1
m
1
¦ x)+c
2
m
2
¦ x)
=c
1
.
1
a
cos
¦
nx
2a
)
+c
2
.
1
a
sin
¦
nx
a
)
1¦ x , t )=c
1
m
1
¦ x) e
−
i E
1
t
ℏ
+c
2
m
2
¦ x) e
−
i E
2
t
ℏ
=
.
1
a
e
−
i E
1
t
ℏ
¦
c
1
cos
¦
n x
2a
)
+c
2
sin
¦
nx
a
)
e
−
i ¦ E
2
−E
1
) t
ℏ
¦
∣1¦ x , t )∣
2
=
1
a
∣
c
1
cos
¦
n x
2a
)
+c
2
sin
¦
nx
a
)
e
−
i ¦ E
2
−E
1
) t
ℏ
∣
2
=
1
a
¦
∣
c
1
∣
2
cos
2
¦
nx
2a
)
+
∣
c
2
∣
2
sin
2
¦
n x
a
)
+2cos
¦
nx
2a
)
sin
¦
nx
a
)
[ c
1
∗
c
2
e
−
i ¦ E
2
−E
1
)t
ℏ

¦
Probability
distribution
in state 1.
Probability
distribution
in state 2.
Oscillates with an angular frequency:
o=
E
2
−E
1
ℏ
2222 Quantum Physics 20067 101
Rate of change of expectation value
Consider the rate of change of the
expectation value of a quantity Q:
d 〈
´
Q〉
d t
=
d
d t
∫
−∞
∞
1
∗
¦
´
Q1
)
dx
=
∫
−∞
∞
¦
d 1
∗
d t
)
¦
´
Q1) dx+
∫
−∞
∞
1
∗
¦
d
´
Q
d t
1
)
dx+
∫
−∞
∞
1
∗
¦
´
Q
d 1
d t
)
dx
=
1
−i ℏ
∫
−∞
∞
¦
´
H 1)
∗
¦
´
Q1) dx+
〈
d
´
Q
d t
〉
+
1
i ℏ
∫
−∞
∞
1
∗
¦
´
Q
´
H 1) dx
´
H and
´
Q are Hermitian ⇒
∫
−∞
∞
¦
´
H 1)
∗
¦
´
Q1) dx=
[
∫
−∞
∞
¦
´
Q1)
∗
´
H 1dx

∗
=
∫
−∞
∞
1
∗
´
H ¦
´
Q1) dx
⇒
d 〈
´
Q〉
d t
=
〈
d
´
Q
d t
〉
+
1
i ℏ
∫
−∞
∞
1
∗
¦
´
Q
´
H−
´
H
´
Q) 1dx
=
〈
d
´
Q
d t
〉
+
1
i ℏ
〈 [
´
Q,
´
H 〉
Comes from intrinsic time
dependence of operator.
Commutator: Comes from the
time dependence of the wave
function.
2222 Quantum Physics 20067 102
Example 1: Conservation of probability
Rate of change of total probability that the
particle may be found at any point:
Total probability conserved (related to existence of a well
defined probability flux – see §3.4)
Total probability is the
“expectation value” of the
operator 1.
6
6t
∫
−∞
∞
∣1∣
2
dx=
6
6t
∫
−∞
∞
1
∗
¦
1×1
)
dx
=
〈
6¦1)
6t
〉
+
1
i ℏ
〈 [ 1 ,
´
H  〉
=0 since the commutator of 1 with any operator is zero: 〈 [ 1,
´
H  〉=
´
H−
´
H=0
⇒
∫
−∞
∞
∣1∣
2
dx=constant
2222 Quantum Physics 20067 103
Example 2: Conservation of energy
Even although the energy of a system may be uncertain (in the sense that measurements of the
energy made on many copies of the system may be give different results) the average energy
is always conserved with time.
Consider the rate of change of the mean energy:
6
6t
〈 E〉 =
6
6t
∫
−∞
∞
1
∗
´
H 1dx =
〈
d
´
H
d t
〉
+
1
i ℏ
〈 [
´
H ,
´
H  〉 =
〈
d
´
H
d t
〉
+0
If Hamiltonian is constant in time, i.e. if
d
´
H
dt
=0
⇒
d 〈 E〉
d t
=0
Conservation of energy provided
Hamiltonian is constant in time.
2222 Quantum Physics 20067 104
5.1 Angular momentum operators
Angular momentum is a very important quantity in three
dimensional problems involving a central force (one that is
always directed towards or away from a central point). In that
case it is classically a conserved quantity:
We can write down a quantummechanical operator for it by applying our usual rules:
Central
point
r
F
The origin of r is the same central
point towards/away from which
the force is directed.
Reading: Rae Chapter 5;
B&J§§6.1,6.3; B&M§§6.26.5
d L
d t
=
d
d t
¦ R×p)=
˙
r×p+r×
˙
p
=
¦
p
m
×p
)
+¦ r×F)=0
´
L=´ r×´p=r×
¦
−i ℏ ∇
)
=
∣
´
i
´
j
´
k
x y z
−i ℏ
d
d x
−i ℏ
d
d y
−i ℏ
d
d z
∣
2222 Quantum Physics 20067 105
5.1 Angular momentum operators (cont.)
Individual components:
´
L
x
=´y p
z
−´z p
y
=−i ℏ
¦
y
6
6 z
−z
6
6 y
)
´
L
y
=´ z p
x
−´x p
z
=−i ℏ
¦
z
6
6 x
−x
6
6 z
)
´
L
z
=´ x p
y
−´y p
x
=−i ℏ
¦
x
6
6 y
−y
6
6 x
)
2222 Quantum Physics 20067 106
5.2 Commutation relations***
Remember:
[ , ]
[ , ]
[ , ]
x
y
z
x p i
y p i
z p i
·
·
·
h
h
h
The different components of angular momentum do
not commute with one another.
By similar arguments get the cyclic permutations:
[
´
L
x
,
´
L
y

=
´
L
x
´
L
y
−
´
L
y
´
L
x
=
¦
´y ´ p
z
−´z ´ p
y
) ¦
´z ´ p
x
−´ x ´ p
z
)
−
¦
´ z ´ p
x
−´x ´ p
z
) ¦
´y ´ p
z
−´z ´ p
y
)
=
¦
´y ´ p
z
´z ´ p
x
−´z ´ p
x
´ y ´ p
z
)
−´y ´ p
z
´ x ´ p
z
+´x ´ p
z
´y ´ p
z
−´z ´ p
y
´ z ´ p
x
+´ z ´ p
x
´z ´ p
y
+
¦
´ z ´ p
y
´x ´ p
z
−´ x ´ p
z
´z ´ p
y
)
=
¦
´y ´ p
z
´z ´ p
x
−´z ´ p
x
´ y ´ p
z
)
+
¦
´z ´ p
y
´ x ´ p
z
−´ x ´ p
z
´z ´ p
y
)
=−
[
´z , ´ p
z

´y ´ p
x
+
[
´z , ´ p
z

´ x ´ p
y
=i ℏ
¦
´x ´ p
y
−´y ´ p
x
)
=i ℏ
´
L
z
[
´
L
x
,
´
L
y

=i ℏ
´
L
z
[
´
L
y
,
´
L
z

=i ℏ
´
L
x
[
´
L
z
,
´
L
x

=i ℏ
´
L
y
2222 Quantum Physics 20067 107
Commutation relations (2)
The different components of L do not commute with one another, but they do commute with
the (squared) magnitude of the angular momentum vector:
Important consequence: we cannot find
simultaneous eigenfunctions of all three
components.
But we can find simultaneous eigenfunctions of one
component (conventionally the z component) and L
2
Note a useful formula:
[ A
2
, B=A
2
B−AB A+AB A−B A
2
=a[ A, B +[ A, B A
´
L
2
=
´
L
x
2
+
´
L
y
2
+
´
L
z
2
Consider:
[
´
L
2
,
´
L
z

=
[
´
L
x
2
,
´
L
z

+
[
´
L
y
2
,
´
L
z

+
[
´
L
z
,
´
L
z

and
[
´
L
x
2
,
´
L
z

=
´
L
x
[
´
L
x
,
´
L
z

+
[
´
L
x
,
´
L
z

´
L
x
=
´
L
x
¦
−i ℏ
´
L
y
)
−i ℏ
´
L
y
´
L
x
=−i ℏ
¦
´
L
x
´
L
y
+
´
L
y
´
L
x
)
Similarly:
[
´
L
y
,
´
L
z

=i ℏ
¦
´
L
x
´
L
y
+
´
L
y
´
L
x
)
⇒
[
´
L,
´
L
z

=
[
´
L
x
2
,
´
L
z

+
[
´
L
y
2
,
´
L
z

=0
2222 Quantum Physics 20067 108
5.3 Angular momentum in spherical polar
coordinates
Spherical polar coordinates are the natural coordinate system in which to
describe angular momentum. In these coordinates,
On this slide, hats refer
to unit vectors, not
operators.
So the full (vector) angular momentum operator
can be written
x
y
z
θ
φ
r
To find zcomponent, note that unit vector k
in zdirection satisfies
(see 2246)
ˆ
r
r · r e
∇=´ e
r
6
6r
+
1
r
´ e
0
6
60
+
1
r sin 0
´ e
!
6
6!
L=−i ℏ r×∇=−i ℏ r ´ e
r
×∇=−i ℏ
∣
´ e
r
´ e
0
´ e
!
r 0 0
6
6r
1
r
6
60
1
r sin 0
6
6!
∣
L=−i ℏ
¦
−´ e
0
1
sin 0
6
6!
+ ´ e
!
6
60
)
´
k⋅´ e
0
=−sin0
´
k⋅ ´ e
!
=0
⇒ L
z
=
´
k⋅L=−i ℏ
6
6!
Note: Has no ´ e
r
component
and doesn't depend on r .
´
k
z
0
´ e
0
n
2
+0
0
2222 Quantum Physics 20067 109
L
2
in spherical polar coordinates
Depends only on angular behaviour of wavefunction. Closely
related to angular part of Laplacian (see 2246 and Section 6).
On this slide, hats refer
to unit vectors, not
operators.
L
2
=L⋅L=−ℏ
2
¦ r×∇)⋅¦ r×∇)
=−ℏ
2
[ r
2
∇
2
−¦ r⋅∇) ¦ ∇⋅r ) 
=−ℏ
2
[
r
2
¦
1
r
2
6
6r
¦
r
2
6
6r
)
+
1
r
2
sin 0
6
60
¦
sin 0
6
60
)
+
1
r
2
sin
2
0
6
2
6!
2
¦
−r
6
6r
¦
6
6r
¦ r)
)

Since ∇
2
=
1
r
2
6
6r
¦
r
2
6
6r
)
+
1
r
2
sin0
6
60
¦
sin0
6
60
)
+
1
r
2
sin
2
0
6
2
6!
2
and radial parts of r
2
∇
2
and ¦ r⋅∇) ¦ ∇⋅r ) cancel.
L
2
=−ℏ
2
[
1
sin0
6
60
¦
sin0
6
60
)
+
1
sin
2
0
6
2
6!
2

∇
2
=
1
r
2
6
6r
¦
r
2
6
6r
)
−
L
2
ℏ
2
r
2
2222 Quantum Physics 20067 110
5.4 Eigenvalues and eigenfunctions
Look for simultaneous eigenfunctions of L
2
and one
component of L (conventional to choose L
z
)
Physical boundary condition: wavefunction
must be singlevalued
Quantization of angular
momentum about zaxis (compare
Bohr model)
Eigenvalues and eigenfunctions of
´
L
z
:
−i ℏ
6
6!
1¦!)=\1¦!)
⇒ 1¦!)=Ae
i \!
ℏ
Note:
´
L
z
only depends on !
1¦!+2n)=1¦!)
Taking our eigenfunction we have:
1¦!+2n)=Ae
I \¦!+2n)
ℏ
=Ae
i \!
ℏ
e
i \2n
ℏ
¦
e
i \2n
ℏ
=1
)
⇒
\
ℏ
=integer , \=mℏ where m is an integer.
1¦!)=Ae
i m!
2222 Quantum Physics 20067 111
Eigenvalues and eigenfunctions (2)
Now look for eigenfunctions of L
2
, in the form
(ensures solutions remain eigenfunctions of L
z
,
as we want)
Eigenvalue condition becomes
f ¦0 , !)=O¦0)1¦!)=e
i m!
O¦0)
´
L
2
[
e
i m!
O¦0)

=ßℏ
2
e
i m!
O¦0) Let eigenvalue =ßℏ
2
⇒ −ℏ
2
[
e
i m!
sin 0
6
60
¦
sin0
6O
60
)
+
O
sin
2
0
6
2
6!
2
¦ e
i m!
)

=ßℏ
2
e
i m!
O¦0)
Divide through by ℏ
2
e
i m!
⇒ −
1
sin0
6
60
¦
sin0
6O
60
)
+
m
2
sin
2
0
O¦0)=ßO¦0)
2222 Quantum Physics 20067 112
The Legendre equation
Make the substitution
This is exactly the Legendre equation, solved in
2246 using the Frobenius method.
u=cos 0
⇒
6
60
=
d u
d 0
6
6u
=−sin 0
6
6u
, and sin
2
0=1−cos
2
0=1−u
2
⇒ Get:
d
d u
[
¦1−u
2
)
d O
d u

+
[
ß−
m
2
1−u
2

O¦0)=0
2222 Quantum Physics 20067 113
Legendre polynomials and associated
Legendre functions
In order for solutions to exist that remain finite at μ=±1 (i.e. at θ=0
and θ=π) we require that the eigenvalue satisfies
The finite solutions are then the associated Legendre functions, which can be
written in terms of the Legendre polynomials:
where m is an integer constrained to lie between –l and +l.
Legendre polynomials:
(like SHO, where we found restrictions on
energy eigenvalue in order to produce
normalizable solutions)
ß=l ¦l +1) , where l =0, 1, 2, 3, 4, ...
P
l
m
¦u)=¦1−u
2
)
∣u∣
2
¦
d
d u
)
∣u∣
P
l
¦u)
P
0
¦u)=1 P
1
¦u)=ui
P
2
¦u)=
1
2
¦3u
2
−1) P
3
¦u)=
1
2
¦5u
3
−3u)
etc.
114
Spherical harmonics
0
0
1
1
0
1
1
1
1
( , )
4
3 3 ( )
( , ) sin exp( )
8 8
3 3
( , ) cos
4 4
3 3 ( )
( , ) sin exp( )
8 8
Y
x iy
Y i
r
z
Y
r
x iy
Y i
r
u o
r
u o u o
r r
u o u
r r
u o u o
r r
·
+
· ·
· ·
· ·
The full eigenfunctions can also be written as spherical harmonics:
Because they are eigenfunctions of Hermitian operators with different eigenvalues, they are
automatically orthogonal when integrated over all angles (i.e. over the surface of the unit
sphere). The constants C are conventionally defined so the spherical harmonics obey the
following important normalization condition:
First few examples (see also 2246):
Remember
sin cos
sin sin
cos
x r
y r
z r
u o
u o
u
·
·
·
Y
l
m
¦0 , !)=c
l m
P
l
m
¦cos 0) e
i m0
¦
c
l m
=¦−1)
m
.
¦l −m)! ¦2l+1)
¦ l+m)! 4n
)
∫
0
n
sin 0d 0
∫
0
2n
d 0
[
Y
l
m
¦0 , !)

∗
Y
l '
m'
¦0 , !)=6
l ,l '
6
m , m'
=
¦
1 if l=l ' and m=m'
0 otherwise
¦
115
Shapes of the spherical harmonics
Imaginary
Real
z
x
y
0
0
1
4
m
l
l
m
Y
r
·
·
·
1
1
3
sin exp( )
8
m
l
l
m
Y i u o
r
·
·
·
1
0
3
cos
4
m
l
l
m
Y u
r
·
·
·
1
1
Y
1
1
Re[ ] Y
0
1
Y
0
0
Y
To read plots: distance from origin corresponds to magnitude (modulus) of
plotted quantity; colour corresponds to phase (argument).
(Images from http://odin.math.nau.edu/~jws/dpgraph/Yellm.html)
116
Shapes of spherical harmonics (2)
(Images from http://odin.math.nau.edu/~jws/dpgraph/Yellm.html)
Imaginary
Real
z
x
y
2
2
0
5
(3cos 1)
16
m
l
l
m
Y u
r
·
·
·
2
1
15
sin cos exp(i )
8
m
l
l
m
Y u u o
r
·
·
·
2
2
2
15
sin exp(2i )
32
m
l
l
m
Y u o
r
·
·
·
1
2
Y
1
2
Re[ ] Y
2
2
Y
2
2
Re[ ] Y
0
2
Y
To read plots: distance from origin corresponds to magnitude (modulus) of
plotted quantity; colour corresponds to phase (argument).
2222 Quantum Physics 20067 117
5.5 The vector model for angular
momentum***
2 2
ˆ
Eigenvalues of are ( 1) , with 0,1, 2, L l l l + · h K
To summarize:
ˆ
Eigenvalues of are , with , , 1, 0,1,
z
L m m l l · + h K K
These states do not correspond to welldefined values of L
x
and L
y
, since these operators
do not commute with L
z
.
l is known as the principal angular momentum quantum number: determines
the magnitude of the angular momentum
m is known as the magnetic quantum number: determines the component of
angular momentum along a chosen axis (the zaxis)
Semiclassical picture: each solution corresponds to a cone of angular momentum
vectors, all with the same magnitude and the same zcomponent.
2222 Quantum Physics 20067 118
The vector model (2)
Example: l=2
Magnitude of angular momentum is
Component of angular momentum in
z direction can be
L
x
L
y
L
z
L
⇒ Eigenvalue of
´
L
2
is l ¦l +1) ℏ
2
=6ℏ
2
.
l ¦l +1) ℏ=
.
6ℏ
2ℏ
ℏ
0
−ℏ
−2ℏ
Reason for restriction on values of m is
so L
z
does not exceed total angular
momentum available.
m=2 ⇒ L
z
=2ℏ
m=1 ⇒ L
z
=ℏ
m=0⇒L
z
=0
m=−1 ⇒ L
z
=−ℏ
m=−2 ⇒ L
z
=−2ℏ
2222 Quantum Physics 20067 119
6.1 The threedimensional square well
Consider a particle which is free to move in three
dimensions everywhere within a cubic box, which
extends from –a to +a in each direction. The particle
is prevented from leaving the box by infinitely high
potential barriers.
x
y
z
Timeindependent Schrödinger equation
within the box is freeparticle like:
Separation of variables: take
x, or y,
or z
( , , ) ( ) ( ) ( ) x y z X x Y y Z z v ·
V ·
V ·
V(x)
a a
0 V ·
with boundary conditions
Reading: Rae §3.2, B&J §7.4; B&M §5.11
X ¦!a)=Y ¦!a)=Z¦!a)=0
−
ℏ
2m
∇
2
m¦ x , y , z )=Em¦ x , y , z)
2222 Quantum Physics 20067 120
Threedimensional square well (2)
Substitute in Schrödinger equation:
Divide by XYZ:
Three effective onedimensional
Schrödinge equations.
−
ℏ
2
2 m
¦
Y Z
d
2
X
d x
2
+Z X
d
2
Y
d y
2
+X Y
d
2
Z
d z
2
¦
=E X Y Z
−
ℏ
2
2m
¦
1
X
d
2
X
d x
2
+
1
Y
d
2
Y
d y
2
+
1
Z
d
2
Z
d z
2
¦
=E
With E=E
x
+E
y
+E
z
−
ℏ
2
2m
d
2
X
d x
2
=E
x
X
−
ℏ
2
2m
d
2
Y
d y
2
=E
y
Y
−
ℏ
2
2m
d
2
Z
d z
2
=E
z
Z
2222 Quantum Physics 20067 121
Threedimensional square well (3)
Wavefunctions and energy eigenvalues known from
solution to onedimensional square well (see §3.2).
Total energy is
E
x
=
n
x
2
n
2
ℏ
2
8ma
2
with n
x
=1, 2, 3, 4, ... Similarly for E
y
and E
z
Note: We have 3 seperate quantum numbers n
x
, n
y
and n
z
E=E
x
+E
y
+E
z
=
n
2
ℏ
2
8ma
2
¦
n
x
2
+n
y
2
+n
z
2
)
This is an example of the power of separation of variables in a 3D problem. Now
we will use the same technique for the hydrogen atom.
2222 Quantum Physics 20067 122
6.2 The Hamiltonian for a hydrogenic
atom***
For a hydrogenic atom or ion having nuclear charge +Ze and a
single electron, the Hamiltonian is
The natural coordinate system to use is spherical polar coordinates. In this case the
Laplacian operator becomes (see 2246):
r
+Ze
Note: for greater accuracy we should use the reduced mass
corresponding to the relative motion of the electron and the nucleus
(since nucleus does not remain precisely fixed – see 1B2x):
e
Note spherical symmetry –
potential depends only on r
This means that the angular momentum about any axis, and also the
total angular momentum, are conserved quantities: they commute
with the Hamiltonian, and can have welldefined values in the
energy eigenfunctions of the system.
Reading: Rae §§3.33.4, B&M Chapter 7, B&J §7.2 and §7.5
´
H=−
ℏ
2
2m
e
∇
2
−
Z e
2
4nc
0
r
u=
m
e
m
N
m
e
+m
N
m
e
= electron mass , m
N
= nuclear mass
∇
2
=
1
r
2
6
6r
¦
r
2
6
6r
)
+
1
r
2
sin0
6
60
¦
sin 0
6
60
)
+
1
r
2
sin
2
0
6
2
6!
2
=
1
r
2
6
6r
¦
r
2
6
6r
)
−
L
2
ℏ
2
r
2
[
´
H ,
´
L
2
=0 ⇔
d 〈
´
L
2
〉
d t
=0
[
´
H ,
´
L
z

=0 ⇔
d
〈
´
L
z
〉
d t
=0
2222 Quantum Physics 20067 123
6.3 Separating the variables
Write the timeindependent Schrődinger equation as:
Now look for solutions in the form
( , , ) ( ) ( , ) r R r Y v u o u o ·
Substituting into the Schrődinger equation:
´
H m¦r , 0, !)=Em¦ r , 0 , !)
⇒ −
ℏ
2
2m
1
r
2
d
d r
¦
r
2
d !
d r
)
+
´
L
2
2mr
2
m−
Z e
2
4nc
0
r
m=Em
−
ℏ
2
2m
Y ¦0, !)
[
1
r
2
d
d r
¦
r
2
d R
d r
)

+
R
2mr
2
´
L
2
Y ¦0, !)−
Z e
2
4nc
0
r
RY =E RY
⇒
1
Y
´
L
2
2m
Y ¦0, !)=Er
2
−
¦
−
ℏ
2
2m
1
R
d
d r
¦
r
2
d R
d r
)
−
Z e
2
r
4nc
0
¦
LHS depends only on 0 and !, RHS depends only on r .
Both sides must equal some constant: \
2222 Quantum Physics 20067 124
The angular equation
We recognise that the angular equation is simply the eigenvalue condition for the
total angular momentum operator L
2
:
This means we already know the corresponding eigenvalues
and eigenfunctions (see §5):
Note: all this would work for any sphericallysymmetric
potential V(r), not just for the Coulomb potential.
1
Y
´
L
2
2m
e
Y=\ ⇒
´
L
2
Y=2m
e
\Y
Y is an eigenfunction of operator
´
L
2
We know
´
L
2
Y
l
m
¦
0, !
)
= l ¦l+1) ℏ
2
Y
l
m
¦
0, !
)
⇒ Angular function Y is a spherical harmonic and \=
l ¦l +1) ℏ
2
2m
e
2222 Quantum Physics 20067 125
6.4 Solving the radial equation
Now the radial part of the Schrődinger equation becomes:
Define a new unknown function χ by:
Note that this depends on l, but not on m: it therefore involves the
magnitude of the angular momentum, but not its orientation.
−
ℏ
2
2m
e
1
R
d
d r
¦
r
2
d R
d r
)
+\=Er
2
+
Z e
2
4nc
0
r
−
ℏ
2
2m
e
1
r
2
d
d r
¦
r
2 d R
d r
)
+
[
l ¦ l+1) ℏ
2
2m
e
r
2
−
Z e
2
4nc
0
r 
R=E R
R¦r)=
X¦ r)
r
⇒
d R
d r
=
1
r
d X
d r
−
X
r
2
⇒ r
2 d R
d r
= r
d X
d r
−X
⇒
d
d r
¦
r
2 d R
d r
)
=r
d
2
X
d r
2
+
d X
d r
−
d X
d r
∴ above becomes: −
ℏ
2
2m
d
2
X
d r
2
+
[
l ¦ l+1) ℏ
2
2m
e
r
2
−
Z e
2
4nc
0
r 
X=EX
2222 Quantum Physics 20067 126
The effective potential
This corresponds to onedimensional motion with the effective potential
First term:
Second term:
V
eff
¦r) =
−Z e
2
4nc
0
r
+
l ¦l +1) ℏ
2
2m
e
r
2
Coulomb attraction:
Force F=−
d V
d r
=
−Z e
2
4nc
0
r
2
'Centrifugal' repulsion:
Force F =−
d V
d r
=
l ¦ l+1) ℏ
2
2m
e
r
2
=
L
2
2m
e
r
2
=
L
2
2 I
= Rotational kinetic energy.
Classically =
¦ m
e
V r)
2
m
e
r
3
=
m
e
V
2
r
r
V(r)
l ¦ l +1) ℏ
2
2m
e
r
2
−Z e
2
4nc
0
r
2222 Quantum Physics 20067 127
Atomic units***
Atomic units: there are a lot of physical constants in these expressions. It makes atomic
problems much more straightforward to adopt a system of units in which as many as
possible of these constants are one. In atomic units we set:
In this unit system, the radial equation becomes
Planck constant ℏ = 1(Dimensions [ M L
2
T
−1
])
Electron mass m
e
= 1(Dimensions [ M ])
Constant appearing in Coulomb's law
e
2
4nc
0
= 1(Dimensions [ M L
3
T
−2
])
It follows that:
Unit of length =
¦
4nc
0
e
2
)
ℏ
2
m
e
= 5.29177×10
−11
m = Bohr radius, a
0
Unit of energy =
¦
e
2
4nc
0
)
2
m
e
ℏ
2
= 4.35974×10
−18
J = 27.21159 eV = Hartree, E
h
−
1
2
d
2
X
d r
2
+
[
l ¦ l+1)
2r
2
−
z
r

X = EX
2222 Quantum Physics 20067 128
Solution near the nucleus (small r)
For small values of r the second derivative and
centrifugal terms dominate over the others.
Try a solution to the differential equation in this limit as
We want a solution such that R(r) remains finite as r→0,
so take
−
1
2
d
2
X
d r
2
+
l ¦l +1)
2r
2
X = 0
X o r
k
⇒ X' ' = k ¦ k−1) r
k−2
and
l ¦ l+1)
r
2
= l ¦ l+1) r
k−2
So: −k ¦ k−1)+l ¦l+1)=0
⇒ k
2
−k−l ¦ l+1)=0
⇒ [ k+l  [ k−¦l+1)=0 ⇒ k=−l or k=l +1
k=¦ l+1) ⇒ X o r
¦ l +1)
as r0 R o r
l
2222 Quantum Physics 20067 129
Asymptotic solution (large r)
Now consider the radial equation at very large distances from the nucleus, when both terms
in the effective potential can be neglected. We are looking for bound states of the atom,
where the electron does not have enough energy to escape to infinity:
Inspired by this, let us rewrite the solution in terms of yet another unknown function,
F(r):
Put: E=−
«
2
2
−
1
2
d
2
X
d r
2
=−
«
2
2
X ⇒
d
2
X
d r
2
=−«
2
X
Solutions: Try X=e
o x
⇒ o
2
=«
2
⇒ o=!«
Take «>0, general solution. X=Ae
«r
+Be
−«r
Ae
«r
term is not normalisable ∴ A=0
X¦r ) = F ¦r ) e
−« r
2222 Quantum Physics 20067 130
Differential equation for F
Can obtain a corresponding differential equation for F:
This equation is solved in 2246, using the
Frobenius (powerseries) method.
The indicial equation gives ( )
or 1 k l l · +
1
regular solution behaves like for small .
l
F r r
+
:
d X
d r
=
d F
d r
e
−«r
−« F e
−«r
d
2
X
d r
2
=
d
2
F
d r
2
e
−«r
−2«
d F
d r
e
−«r
+«
2
F e
−«r
Substituting in SE and cancelling factors of E
−«r
gives:
−
1
2
d
2
F
d r
2
+ «
d F
d r
−
1
2
«
2
F+
[
l ¦l +1)
2r
2
−
Z
r

F =−
1
2
«
2
F ⇒
d
2
F
d r
2
−
l ¦l +1)
r
2
F = 2«
d F
d r
−2
Z
r
F
F¦ r) = r
k
∑
p
a
p
r
p
= ∑
p
a
p
r
p+k
2222 Quantum Physics 20067 131
Properties of the series solution
where is an integer : 1, 2
Z
n n l n l l
x
· > · + + K
Hence the series must terminate after a finite number of terms. This happens only if
So the energy is
If the full series found in 2246 is allowed to continue up to an arbitrarily large number of
terms, the overall solution behaves like
Note that once we have chosen n, the energy is independent of both m (a feature of all
spherically symmetric systems, and hence of all atoms) and l (a special feature of the
Coulomb potential, and hence just of hydrogenic atoms).
n is known as the principal quantum number. It defines the “shell structure” of the
atom.
(not normalizable)
F¦ r)≈e
2«r
⇒ X¦ r)≈e
2«r
e
−«r
= e
«r
E =−
1
2
«
2
=−
1
2
¦
Z
n
)
2
2222 Quantum Physics 20067 132
6.5 The hydrogen energy spectrum and wavefunctions***
2
2
(in atomic units)
2
n
Z
E
n
·
, ( 1), 0, ( 1), m l l l l · K K
For each value of n=1,2,… we have a definite
energy:
For each value of n, we can have n possible values of
the total angular momentum quantum number l:
For each value of l and n we can have 2l+1 values of
the magnetic quantum number m:
l=0,1,2,…,n1
The total number of states (statistical weight) associated
with a given energy E
n
is therefore
Traditional nomenclature:
l=0: s states (from “sharp” spectral lines)
l=1: p states (“principal”)
l=2: d states (“diffuse”)
l=3: f states (“fine”)
…and so on alphabetically (g,h,i… etc)
Each solution of the timeindependent Schrődinger equation is
defined by the three quantum numbers n,l,m
E
¦
in units
Z
2
2
E
h
)
∑
l =0
n−1
¦ 2l +1)=n
2
l=0 l=1 l=2 l=3
0
1
−
1
4
−
1
9
−
1
16
all
x3
all
x5
all
x7
2 p ⇒ n=2 , l =1
3 s ⇒ n=3 , l =0
2222 Quantum Physics 20067 133
The radial wavefunctions
Radial wavefunctions R
nl
depend on principal
quantum number n and angular momentum quantum
number l (but not on m)
Full wavefunctions are:
Normalization chosen so that:
Note:
Probability of finding electron between radius r and r+dr is:
Only s states (l=0) are finite at the
origin.
Radial functions have (nl1) zeros.
R
10
¦ r)=2
¦
Z
a
0
)
3
2
e
−Z r
a
0
R
21
¦r)=
1
.
3
¦
Z
2a
0
)
3
2
¦
Z r
a
0
)
e
−Z r
2a
0
R
20
¦r)=2
¦
Z
2a
0
)
3
2
¦
1−
Z r
2a
0
)
e
−Z r
2a
0
R
32
¦r)=
4
27.10
¦
Z
3a
0
)
3
2
¦
Z r
a
0
)
2
e
−Z r
3a
0
R
31
¦ r)=
4
.
2
9
¦
Z
3a
0
)
3
2
¦
1−
Z r
6a
0
)¦
Z r
a
0
)
e
−Z r
3a
0
R
30
¦ r)=2
¦
Z
3a
0
)
3
2
¦
1−
2 Z r
3a
0
+
2 Z
2
r
2
27a
0
2
)
e
−Z r
3a
0
m
nl m
¦ r , 0 , !)=R
n l
¦ r) Y
l
m
¦0 , !)
∫
0
∞
r
2
R
nl
2
¦r) dr∫
0
n
sin¦0) d 0 ∫
0
2n
d !∣Y
l
m
¦0, !)∣
2
=1
But: ∫
0
n
sin¦0) d 0 ∫
0
2n
d !∣Y
l
m
¦0, !)∣
2
=1 for spherical harmonics.
⇒ ∫
0
∞
r
2
R
nl
2
¦ r) dr=1
r
2
R
nl
2
¦ r)=X
nl
¦ r) since: X
nl
=r R
nl
¦ r)
i.e. r
2
R
nl
¦r) is the probability per unit length of finding the
electron at a radius r . NOT the probability per unit volume of
finding the particle at a given point in space: ∣m
nl m
∣
2
2222 Quantum Physics 20067 134
Comparison with Bohr model***
, 1, 2, 3,
z
L n n · · h K
2
0
0
, Bohr radius
n
n a
r a
Z
· ·
Angular momentum (about any axis)
assumed to be quantized in units of
Planck’s constant:
Electron otherwise moves according
to classical mechanics and has a
single welldefined orbit with radius
Energy quantized and determined
solely by angular momentum:
Bohr model Quantum mechanics
2
2
, Hartree
2
n h h
Z
E E E
n
· ·
, , ,
z
L m m l l · · h K
0
2
0
1
, Bohr radius
Z
a
r
n a
· ·
2
2
, Hartree
2
n h h
Z
E E E
n
· ·
Angular momentum (about any axis) shown
to be quantized in units of Planck’s
constant:
Energy quantized, but is determined
solely by principal quantum number,
not by angular momentum:
Electron wavefunction spread over all
radii. Can show that the quantum
mechanical expectation value of the
quantity 1/r satisfies
2222 Quantum Physics 20067 135
6.6 The remaining approximations
• This is still not an exact treatment of a real H atom, because we have
made several approximations.
– We have neglected the motion of the nucleus. To fix this we would need to
replace m
e
by the reduced mass μ (see slide 1).
– We have used a nonrelativistic treatment of the electron and in particular have
neglected its spin (see §7). Including these effects gives rise to
• “fine structure” (from the interaction of the electron’s orbital motion with its spin), and
• “hyperfine structure” (from the interaction of the electron’s spin with the spin of the
nucleus)
– We have neglected the fact that the electromagnetic field acting between the
nucleus and the electron is itself a quantum object. This leads to “quantum
electrodynamic” corrections, and in particular to a small “Lamb shift” of the
energy levels.
2222 Quantum Physics 20067 136
7.1 Atoms in magnetic fields
Interaction of classically orbiting
electron with magnetic field:
v
Orbit behaves like a current loop:
In the presence of a magnetic field B, classical interaction energy is:
r
Corresponding quantum mechanical expression (to a good approximation) involves the
angular momentum operator:
μ
Reading: Rae Chapter 6; B&J §6.8, B&M Chapter 8 (all go further than 2B22)
Loop current =
−e v
2nr
( ve sign because chage =−e)
Magnetic moment u= current × area
=
¦
−e v
2nr
)
nr
2
=
−e
2m
e
m
e
v r=−u
B
L
ℏ
Where u
B
=
e ℏ
2m
e
(The Bohr magneton)
AE = −u ⋅ B = u
B
L
ℏ
⋅ B
Contribution to Hamiltonian involving B = A
´
H =
u
B
ℏ
¦ L ⋅ B)
2222 Quantum Physics 20067 137
Splitting of atomic energy levels
Suppose field is in the z direction. The Hamiltonian operator is
0
ˆ ˆ ˆ
B z
z
B
H H L
µ
· +
h
We chose energy eigenfunctions of the original atom that are eigenfunctions of L
z
so these
same states are also eigenfunctions of the new H.
0 0
ˆ
;
ˆ
.
m m
z m m
H E
L m
v v
v v
·
· h
⇒
´
H m
m
=
´
H
0
m
m
+
u
B
B
z
ℏ
´
L
z
m
m
=
¦
E
0
+mu
B
B
z
)
m
m
New
eigenvalue.
2222 Quantum Physics 20067 138
Splitting of atomic energy levels (2)
0 B ·
Predictions: should always get an odd number of
levels. An s state (such as the ground state of
hydrogen, n=1, l=0, m=0) should not be split.
(2l+1) states with same
energy: m=l,…+l
(Hence the name
“magnetic quantum
number” for m.)
0 B
E=E
0
m=l E=E
0
+l u
B
B
z
m=¦l −1)
m=−l E=E
0
−l u
B
B
z
2222 Quantum Physics 20067 139
7.2 The SternGerlach experiment***
Study deflection of atoms in inhomogeneous magnetic field. Force on
atoms is
Gerlach
N
S
Produce a beam of atoms with a single electron in an s state (e.g.
hydrogen, sodium)
Results show two groups of atoms, deflected in
opposite directions, with magnetic moments
Consistent neither with classical physics (which would predict a
continuous distribution of μ) nor with our quantum mechanics so
far (which always predicts an odd number of groups, and just one
for an s state).
F=∇
¦
u⋅ B
)
⇒ if u is aligned with B, the atom is pushed towards high fields.
If u is antialigned with B atom is pushed towards low fields.
u =!u
B
140
7.3 The concept of spin***
Try to understand these results by analogy with what we know about the ordinary (“orbital”)
angular momentum: must be due to some additional source of angular momentum that does
not require motion of the electron. Known as “spin”.
Introduce new operators to represent spin, assumed to have same
commutation relations as ordinary angular momentum:
Goudsmit Uhlenbeck
Corresponding eigenfunctions and eigenvalues:
Pauli
(will see in Y3 that these equations can be derived
directly from the commutation relations)
[
´
S
x
,
´
S
y

=i ℏ
´
S
z
etc. Where ¦
´
S
x
,
´
S
y
,
´
S
z
) are components of spin angular momentum.
Define:
´
S
2
=
´
S
x
2
+
´
S
y
2
+
´
S
z
2
´
S
2
= X
s
m
s
= s ¦ s+1) ℏ
2
X
s
m
s
m
s
= magnetic spin quantity
´
S
z
X
s
m
s
=m
s
ℏ X
s
m
s
Find S does not have to be an integer, but can be an
integer or half integer and m
s
can vary from +S to −S
in integer steps.
2222 Quantum Physics 20067 141
Spin quantum numbers for an electron
General interaction with magnetic field:
From the SternGerlach experiment, we know that electron spin along a
given axis has two possible values.
So, choose
So, have
Spin angular momentum is
twice as “effective” at
producing magnetic moment as
orbital angular momentum.
S=
1
2
⇒ m
s
=−s..........+s − !
1
2
But we also know from SternGerlach that magnetic moments associated with
the two possibilities are u = ! u
B
u = ! 2m
s
u
B
´
H =
´
H
0
+
u
B
ℏ
B ⋅ ¦
´
L ⋅ g
´
S)
g=2(Dirac's relativistic theory)
g=2.00231930437(Quantum Electrodynamics)
g=g factor (Measures how effective this particular form of angular momentum is at
producing a magnetic moment.)
2222 Quantum Physics 20067 142
A complete set of quantum numbers
Hence the complete set of quantum numbers for the electron in the H atom is: n,l,m,s,m
s.
Corresponding to a full wavefunction
Note that the spin functions χ do not depend on the electron coordinates r,θ,φ; they
represent a purely internal degree of freedom.
H atom in magnetic field, with spin included, and field in the z direction:
m
n , l , m, s , m
s
¦
r , 0, !
)
= R
n , l
¦ r ) Y
l
m
¦
0, !
)
X
S
m
s
i.e. 2 states, with m
s
=!
1
2
for each one we found before.
´
H =
´
H
0
+
u
B
B
z
ℏ
¦
´
L
z
+g
´
S
z
)
⇒ Change in energy is u
B
B
z
¦
m+g m
s
)
≃ u
B
B
z
¦
m+2m
s
)
For ground state ¦l =0, m=0) , get AE = ! u
B
B
z
as observed.
143
7.4 Combining different angular momenta
1 1
2 2
,
, ,
j
j l l
m j j
· +
· + K
So, an electron in an atom has two sources of angular momentum:
•Orbital angular momentum (arising from its motion through the
atom)
•Spin angular momentum (an internal property of its own).
To think about the total angular momentum produced by
combining the two, use the vector model once again:
L
x
L
y
L
z
Vector addition between orbital angular
momentum L (of magnitude L) and spin S (of
magnitude S): produces a resulting angular
momentum vector J: quantum mechanics says its
magnitude lies somewhere between LS and
L+S.(in integer steps).
L
S
L+S
LS
For a single electron, corresponding `total
angular momentum’ quantum numbers are
Determines length of resultant
angular momentum vector
Determines orientation
· + J L S
L
S
Eigenvalues of
´
J = j ¦ j+1) ℏ
2
Eigenvalue of
´
J
z
=m
j
ℏ
m
j
=3/ 2
m
j
=1/2
m
j
=−1/ 2
m
j
=−3/ 2
e.g. l =1 , j=
3
2
,
1
2
2222 Quantum Physics 20067 144
Example: the 1s and 2p states of hydrogen
The 1s state:
The 2p state:
l =0 , s=
1
2
⇒ 1 possibility j=
1
2
Purely spin angular momentum. m
j
=!
1
2
¦ n=2) , l=1 , S=
1
2
Now 2 possibilities: j=
1
2
,
3
2
; m
j
=
¦
−
1
2
,
1
2
)
,
¦
−
3
2
, −
1
2
,
1
2
,
3
2
)
⇒ Get a doublet of states adding 2 different values of m
j
, and a quartet of states
adding 4 different values of m
j
Even in no B  field. j=
1
2
and j=
3
2
states have different energies.
(Fine structure effects.)
2222 Quantum Physics 20067 145
Combining angular momenta (2)
The same rules apply to combining other angular momenta, from whatever source.
For example for two electrons in an excited state of He atom, one in 1s state and one in 2p state
(defines what is called the 1s2p configuration in atomic spectroscopy):
First construct combined orbital angular momentum L of both electrons:
Then construct combined spin S of both electrons:
Hence there are two possible terms (combinations of L and S):
…and four levels (possible ways of combining L and S to get different total angular
momentum quantum numbers)
1 1
1 1 2 2 2 2
0; ; 1; l s l s · · · ·
L must be between
∣
L
1
−L
2
∣
=1 and L
1
+L
2
=1
⇒ S=0, 1
∣
S
1
+S
2
∣
=0 and S
1
+S
2
=1
⇒ S=0, 1
L=1 , S=0 ⇒ J =1
L=1 , S=1 ⇒ J =0 , 1, 2
2222 Quantum Physics 20067 146
Term notation
Spectroscopists use a special notation to describe terms and levels:
2 1 S
J
L
+
•The first (upper) symbol is a number giving the number of spin states
corresponding to the total spin S of the electrons
•The second (main) symbol is a letter encoding the total orbital angular momentum
L of the electrons:
•S denotes L=0
•P denotes L=1
•D denotes L=2 (and so on);
•The final (lower) symbol gives the total angular momentum J obtained from
combining the two.
Example: terms and levels from previous page would be:
L=1 , S=0 ⇒
1
P
1
(Singlet)
L=1 , S=1 ⇒
3
P
0
,
3
P
1
,
3
P
2
2222 Quantum Physics 20067 147
7.5 Wavepackets and the Uncertainty Principle
revisited (belongs in §4 – nonexaminable)
Can think of the Uncertainty Principle as arising from the structure of wavepackets. Consider a
normalized wavefunction for a particle located somewhere near (but not exactly at) position x
0
Can also write this as a Fourier transform (see 2246):
2
( ) k v%
Probability density:
k
(expansion in eigenstates of momentum)
m¦ x)=
¦
2nc
2
)
−
1
4
exp
[
−¦ x−x
0
)
2
4c
2

∣m¦ x)∣
2
=
¦
2nc
2
)
−
1
2
exp
[
−¦ x−x
0
)
2
2c
2

2
( ) x v
x
x
0
c=
standard
deviation.
m¦ x)=
1
.
2n
∫
−∞
∞
m¦ k ) e
i k x
dk
2222 Quantum Physics 20067 148
7.5 Wavepackets and the Uncertainty Principle revisited
(belongs in §4 – nonexaminable) (cont.)
Compare m¦ x)=∑a
n
!
n
¦ x)
then m¦ k)=
1
.
2n
∫
−∞
∞
m¦ x) e
−i k x
dx
Compare a
n
=∫
−∞
∞
m¦ x) !
∗
¦ x) dx
e
i k x
⇒ !
n
¦ x) (Eigenfunction)
¯
m¦ k) (Expansion coefficient)
2222 Quantum Physics 20067 149
Fourier transform of a Gaussian
¯ m¦ k )=
1
.
2n
∫
−∞
∞
m¦ x) exp[−i k x dx
=
1
.
2n
¦ 2nc
2
)
−
1
4
∫
−∞
∞
exp
[
−
¦ x−x
0
)
2
4c
2

exp[−i k x dx
=
1
.
2n
¦ 2nc
2
)
−
1
4
exp
[
−i k x
0
 ∫
−∞
∞
exp
[
−
¦ x−x
0
)
2
4 c
2
−i k ¦ x−x
0
)

dx
=
1
.
2n
¦ 2nc
2
)
−
1
4
exp
[
−i k x
0
 ∫
−∞
∞
exp
[
−
[¦ x−x
0
)+2i k c
2

2
4c
2
−k
2
c
2

dx
=
1
.
2n
¦ 2nc
2
)
−
1
4
exp
[
−i k x
0

exp[−k
2
c
2
 ∫
−∞
∞
exp
[
−
x '
2
4c
2

dx With: x ' =x−x
0
+2i k c
2
, dx ' =dx
=
1
.
2n
¦ 2nc
2
)
−
1
4
exp
[
−i k x
0

exp[−k
2
c
2
 .
n2c
=
¦
n
2c
2
)
−
1
4
exp
[
−i k x
0

exp [−k
2
c
2

∣¯ m¦k )∣
2
=
¦
n
2c
2
)
−
1
2
exp [−2 k
2
c
2

∫
−∞
∞
∣¯ m¦k )∣
2
dk=
.
n
2c
2
¦
n
2c
2
)
−
1
2
=1 ∫
−∞
∞
exp
[
−
x
2
a
2

dx=
.
na , ∫
−∞
∞
x
2
exp
[
−
x
2
a
2

dx=
.
na
3
2
2222 Quantum Physics 20067 150
Wavepackets and Uncertainty Principle (2)
In fact, can show that this form of wavepacket (“Gaussian wavepacket”) minimizes the
product of Δx and Δp, so:
Meansquared uncertainty in postion
Meansquared uncertainty in momentum:
Mean momentum:
Ax
2
=
〈 ¦
x−x
0
)
2
〉
=
∫
−∞
∞
¦
x−x
0
)
2
∣m¦ x)∣
2
dx=c
2
p=ℏ k ∣
¯ m¦ k )∣
2
is symmetric about k =0 ⇒ 〈 p〉 =0
A p
2
=〈 p
2
〉=ℏ
2
〈 k
2
〉=
ℏ
2
4c
2
⇒ Ax
2
A p
2
=c
2
ℏ
2
4c
2
=
ℏ
2
4
Ax A p ¯
ℏ
2
Rigorous statement of
uncertainty principle for
position and momentum.
2222 Quantum Physics 20067 151
Wavepackets and Uncertainty Principle (3)
Summary
Three ways of thinking of Uncertainty principle:
(3) Arising from the physics of the interaction of different types of measurement apparatus with the
system (e.g. in the gammaray microscope);
(4) Arising from the properties of Fourier transforms (narrower wavepackets need a wider range of
wavenumbers in their Fourier transforms);
(5) Arising from the fact that x and p are not compatible quantities (do not commute), so they
cannot simultaneously have precisely defined values.
General result (see third year, or Rae §4.5):
For general noncommuting operators
´
Q ,
´
R
AqAr ¯
1
2
∣〈 [
´
Q ,
´
R 〉∣
Where: Aq and Ar are RMS uncertainties in
´
Q and
´
R
Prerequisites
Firstyear Mathematics for Physics and Astronomy (1B45 and 1B46) or equivalent Material from the secondyear maths course (2246) will be used after it has been covered in that course Basic relativistic kinematics (from 1B46) will be assumed, and basic electromagnetism (field and potential of point charge, interaction of magnetic dipole with magnetic field) will be used as it is covered in 2201
2222 and other courses
Some limited overlap with 1B23 Modern Physics, Astronomy and Cosmology (bur different approach – 2222 is less descriptive and more rigorous). Areas covered by both courses: o Waveparticle duality (photoelectric effect, doubleslit experiment) o Timeindependent Schrődinger equation o Significance of wave function and Heisenberg’s Uncertainty Principle 1B23 is not a prerequisite for 2222!
2222 Quantum Physics 20067 2
Syllabus
1. The failure of classical mechanics [3 lectures] Photoelectric effect, Einstein’s equation, electron diffraction and de Broglie relation. Compton scattering. Waveparticle duality, Uncertainty principle (Bohr microscope). 2. Steps towards wave mechanics [3 lectures] Timedependent and timeindependent Schrödinger equations. The wave function and its interpretation. 3. Onedimensional timeindependent problems [7 lectures] Infinite square well potential. Finite square well. Probability flux and the potential barrier and step. Reflection and transmission. Tunnelling and examples in physics and astronomy. Wavepackets. The simple harmonic oscillator. 4. The formal basis of quantum mechanics [5 lectures] The postulates of quantum mechanics – operators, observables, eigenvalues and eigenfunctions. Hermitian operators and the Expansion Postulate. 5. Angular momentum in quantum mechanics [2 lectures] 2 ˆ ˆ Operators, eigenvalues and eigenfunctions of L and L . z
2222 Quantum Physics 20067
3
L.Syllabus (contd) 6. Total spin and orbital angular momentum quantum numbers S. Three dimensional problems and the hydrogen atom [4 lectures] Separation of variables for a threedimensional rectangular well. 2222 Quantum Physics 20067 4 . The radial Schrödinger equation. Construct J from S and L. Separation of space and time parts of the 3D Schrödinger equation for a central field. Electron spin and total angular momentum [3 lectures] Magnetic moment of electron due to orbital motion. J. and casting it in a form suitable for solution by series method. 7. The SternGerlach experiment. Rules for addition of angular momentum quantum numbers. Electron spin and complete set of quantum numbers for the hydrogen atom. Degeneracy and spectroscopic notation.
commutators. E 1Z 2 n2 Yl m ( . Born interpretation Separation of variables 2246 Maths Methods III Timeindependent Schrödinger Frobenius equation method Quantum simple harmonic oscillator Hydrogenic atom Postulates: Operators. expansions in complete sets.eigenvalues and eigenfunctions.Photoelectric effect. doubleslit experiment Particle nature of light in quantum mechanics Wave nature of matter in quantum mechanics Timedependent Schrödinger equation. Compton scattering E h h p Waveparticle duality DavissonGermer experiment. ) 2222 Quantum Physics 20067 ˆ ˆ Lz . expectation values. time evolution Legendre equation E n = n 1D problems 2246 1 ℏ 0 2 Radial solution Angular solution 2 Angular momentum operators Rnl . L2 5 .
Lecture style • Experience (and feedback) suggests the biggest problems found by students in lectures are: – Pacing of lectures – Presentation and retention of mathematically complex material • Our solution for 2222: – Use powerpoint presentation via data projector or printed OHP for written material and diagrams – Use whiteboard or handwritten OHP for equations in all mathematically complex parts of the syllabus – Student copies of notes will require annotation with these mathematical details – Notes (unannotated) will be available for download via website or (for a small charge) from the Physics & Astronomy Office • Headings for sections relating to key concepts are marked with asterisks (***) 2222 Quantum Physics 20067 6 .
while electrons absorb enough energy to escape from material 2222 Quantum Physics 20067 7 . expect a time lag between light exposure and emission.2 Hertz J. frequency ν Electric field E of light exerts force F=Vacuum eE on electrons.J. emits charged particles (Hertz 1887).1.J. plate plate Electrons should be emitted whatever the frequency ν of the light. B&J §1.5. Thomson 1. force increases. Rae §1. which were subsequently shown to be electrons by J. As intensity of light chamber increases.1 Photoelectric effect Metal plate in a vacuum. Thomson (1899). so KE of Collecting Metal ejected electrons should increase.B&M §2. irradiated by ultraviolet light. so long as E is sufficiently large I Ammeter Potentiostat For very low intensities. Classical expectations Light.
Einstein’s interpretation (1905): light is emitted and absorbed in packets (quanta) of energy Millikan E h (1.2) Planck constant: universal constant of nature Work function: minimum energy needed for electron to escape from metal (depends on material. However. but dependent on ν For ν<ν0 (i. for frequencies below a cutoff frequency) no electrons are emitted There is no time lag. rate of ejection of electrons depends on light intensity.Einstein Photoelectric effect (contd)*** Actual results: Maximum KE of ejected electrons is independent of intensity.63×10−34 Js .e. but usually 25eV) 2222 Quantum Physics 20067 Verified in detail through subsequent experiments by Millikan 8 h=6.1) An electron absorbs a single quantum in order to leave the material The maximum KE of an emitted electron is then predicted to be: K max h W (1.
Photoemission experiments today Modern successor to original photoelectric effect experiments is ARPES (AngleResolved Photoemission Spectroscopy) Emitted electrons give information on distribution of electrons within a material as a function of energy and momentum 2222 Quantum Physics 20067 9 .
) 10 2222 Quantum Physics 20067 .Frequency and wavelength for light*** Relativistic relationship between a particle’s momentum and energy: For massless particles propagating at the speed of light. becomes E 2 p 2 c 2 m0 2 c 4 E 2 p 2c 2 E =c∣ p∣ h=c∣ p∣ Hence find relationship between momentum p and wavelength λ: ∣ p∣= But: h c =c ∣ p∣= h (For light.
as function of wavelength for different angles.2 Compton scattering Collimator (selects angle) Crystal (selects wavelength) Compton (1923) measured scattered intensity of Xrays (with welldefined wavelength) from solid target. B&J §1. Phys. Xray source θ Target Result: peak in the wavelength distribution of scattered radiation shifts to longer wavelength than source. 22 409 (1923) 11 2222 Quantum Physics 20067 .H. by an amount that depends on the scattering angle θ (but not on the target material) Detector A. Rev. Compton.7.3 1. Rae §1.2.Compton B&M §2.
Classical picture: oscillating electromagnetic field would cause oscillations in positions of charged particles. p− p ' =∣ p2∣∣ p ' 2∣ −2∣ p∣∣ p '∣ cos Write in terms of momentum: 2 2 2 2 h m e c =h ' p e c me c pcme c = p ' c p e c me c 2 2 2 2 1 4 2 1 4 2 p− p ' cm e c = p e c m e c 2 2 2 4 3 2 2 4 p− p' c me c 2 p− p ' me c = p c me c p− p ' 2 p− p ' me c= pe 2 2 ∣ pe 2∣= p− p ' 2 2 1−cos pp ' 2222 Quantum Physics 20067 12 . reradiation in all directions at same frequency and wavelength as incident radiation Incoming photon p Frequency Compton scattering (contd) Photon After Electron pe θ φ p’ Before Compton’s explanation: “billiard ball” collisions between Xray photons and electrons in the material Conservation of energy: 2 2 2 1 2 4 2 Conservation of momentum: In electrons initial rest frame: p= p ' p e p e= p− p ' ∣ pe 2∣ = p− p ' .
0243 Å) 13 2222 Quantum Physics 20067 .3) me c ⇒ ' −=1−cos h h ' (1 cos ) (1.4) me c ‘Compton wavelength’ of electron (0.Compton scattering (contd) Equate above for p e 2 : 2 2 p− p ' 2 p− p ' m e c= p− p ' 21−cos pp ' ⇒ p− p ' m e c=1−cos pp' 1 1 ⇒ me c − =1−cos p' p Assuming photon momentum related to wavelength: h p (1.
p=ℏk ℏ 2m Second peak at original due to nuclei collisions. 2222 Quantum Physics 20067 14 . 2mE ℏ2 k 2 =±ikwherek 2= 2 or =E kis DeBroglie wavenumber.Puzzle What is the origin of the component of the scattered radiation that is not wavelengthshifted? ℏ2 2 x x ℏ2 2 2 2mE Substitute: − e =Ee ⇒ − =E ⇒ =− 2 2m 2m ℏ ⇒ Assuming E0 RHS is ve is imaginary.
Einstein (1924) •Light exhibits diffraction and interference phenomena that are only explicable in terms of wave properties •Light is always detected as packets (photons).e. to square of electromagnetic field strength) 2222 Quantum Physics 20067 15 . both indispensable.” A.Waveparticle duality for light*** “ There are therefore now two theories of light.without any logical connection.as one must admit today despite twenty years of tremendous effort on the part of theoretical physicists . and . we never observe half a photon •Number of photons proportional to energy density (i. if we look.
de Broglie Proposal: dual waveparticle nature of radiation also applies to matter. it was certain in the course of summer 1923 . And I realised that.4.” L. on the other hand. which are rarely found in mechanics but occur very frequently in wave phenomena and in all problems dealing with wave motion. the HamiltonJacobi theory pointed somewhat in that direction..B&M §4.. in quantum phenomena one obtains quantum numbers. it represents a geometrical optics. for it can be applied to particles and. thus suddenly . Rae §1. Any object having momentum p has an associated wave whose wavelength λ obeys h p= =ℏ k 2 k (wavenumber) h ℏ= 2 Prediction: crystals (already used for Xray diffraction) might also diffract particles 2222 Quantum Physics 20067 16 .I got the idea that one had to extend this duality to material particles. B&J §1. on the one hand.12. in addition..3 Matter waves*** “As in my conversations with my brother we always arrived at the conclusion that in the case of Xrays one had both waves and corpuscles. especially to electrons.6 De Broglie 1.
Electron diffraction from crystals Thomson Davisson G. J..P.e. "Are Electrons Waves?. θi The DavissonGermer experiment (1927): scattering a beam of electrons from a Ni crystal θr At fixed angle. 597 (1928) At fixed accelerating voltage (i. Thomson performed similar interference experiments with thinfilm samples 2222 Quantum Physics 20067 17 ." Franklin Institute Journal 205. fixed electron energy) find a pattern of pencilsharp reflected beams from the crystal G. find sharp peaks in intensity as a function of electron energy Davisson. C.P.
19151923) θi Path difference: a cos i θr a cos r −a cos i a cos r −cos i Constructive interference when Lawrence Bragg a cos r −cos i =n Modern Low Energy Electron Diffraction (LEED): this pattern of “spots” shows the beams of electrons produced by surface scattering from complex (7×7) reconstruction of a silicon surface 18 a Electron scattering dominated by surface layers Note θi and θr not necessarily equal a cos r Note difference from usual “Bragg’s Law” geometry: the identical scattering planes are oriented perpendicular to the surface 2222 Quantum Physics 20067 . UCL.Electron diffraction from crystals (contd)pioneered for scattering Interpretation used similar ideas to those of Xrays from crystals by William and Lawrence Bragg William Bragg (Quain Professor of Physics.
y d Incoming beam of particles (or light) θ Alternative method of detection: scan a detector across the plane and record arrivals at each point d sin D 2222 Quantum Physics 20067 Detecting screen (scintillators or particle detectors) 19 .The doubleslit interference experiment Originally performed by Young (1801) with light. Subsequently also performed with many types of matter particle (see references).
L.Results Neutrons. Hackermüller et al. 1988 Reviews of Modern Physics 60 10671073 He atoms: O Carnal and J Mlynek 1991 Physical Review Letters 66 26892692 Fringe visibility decreases as molecules are heated. A Zeilinger et al. 2004 Nature 427 711714 C60 molecules: M Arndt et al. 1999 Nature 401 680682 With multipleslit grating Without grating 2222 Quantum Physics 20067 20 .
with d=8μm and D=64cm ⇒ Maximum at y n = D tan n≈ D n ≈ D ⇒ Spacing at d n D d p2 3 Expect: = K T 2m 2 B ⇒ 2222 Quantum Physics 20067 h p=4.24×10 m d ⇒ 21 .Doubleslit experiment: interpretation Interpretation: maxima and minima arise from alternating constructive and destructive interference between the waves from the two slits Spacing between maxima: Constructive interference: d sin =n ⇒ n th maximum occurs at: d sin n =n For small .8×10−24 Ns⇒ = =1.sin ≈tan n n≈ d Example: He atoms at a temperature of 83K.03 Å p D −6 Spacing = =8.
page 15) and at http://physicsweb. 2004 Nature 427 711714) An excellent summary is available in Physics World (September 2002 issue. 1988 Reviews of Modern Physics 60 10671073) • Performed with He atoms (O Carnal and J Mlynek 1991 Physical Review Letters 66 26892692) • Performed with C60 molecules (M Arndt et al. translated 1974 American Journal of Physics 42 411) • Performed with single electrons (A Tonomura et al.org/ (readers voted the doubleslit experiment “the most beautiful in physics”). 1999 Nature 401 680682) • Performed with C70 molecules. 1989 American Journal of Physics 57 117120) • Performed with neutrons (A Zeilinger et al. 2222 Quantum Physics 20067 22 . showing reduction in fringe visibility as temperature rises so molecules “give away” their position by emitting photons (L. Hackermüller et al.Doubleslitdevelopment of the doubleslit experiment during the experiment: bibliography Some key papers in the 20th century: • Performed with a light source so faint that only one photon exists in the apparatus at any one time (G I Taylor 1909 Proceedings of the Cambridge Philosophical Society 15 114115) • Performed with electrons (C Jönsson 1961 Zeitschrift für Physik 161 454474.
so wave is a property of a single particle – A particle can “interfere with itself” Wavelength unconnected with internal lengthscales of object.g. if we look. we never observe half an electron •Number of particles proportional to….??? 2222 Quantum Physics 20067 23 . determined by momentum Attempt to find out which slit particle moves through causes collapse of interference pattern (see later…) Waveparticle duality for matter particles •Particles exhibit diffraction and interference phenomena that are only explicable in terms of wave properties •Particles always detected individually.Matter waves: key points*** • • • Interference occurs even when only a single particle (e. photon or electron) in apparatus.
involves uncertainty: we only know the probability that the particle will be found near a particular location. Screen forming image of particle Particle θ/2 Light source.4 Heisenberg’s gammaray microscope and a first look at the Uncertainty Principle The combination of wave and particle pictures. having angular diameter θ Resolving power of lens: y y 2222 Quantum Physics 20067 Heisenberg 24 . Rae §1. wavelength λ Lens.5 (first part only) 1.5. and in particular the significance of the ‘wave function’ in quantum mechanics (see also §2).B&M §4.5. B&J §2.
⇒ Partice momentum must lie Neglecting Compton in the same range: effect. if they have initial momentum p: Ycomponent of momentum after scattering.) (Small angle/small lens) p y =2psin ≃ p 2 Remember resolution power of y p y h lens from classical optics: Heisenberg’s Uncertainty y Principle 2222 Quantum Physics 20067 y p y h 25 .Heisenberg’s gammaray microscope and the Uncertainty Principle*** Range of ymomenta of photons after scattering. θ/2 p p Py px − psin p y psin (Assuming magnitude of 2 2 p unchanged i.e.
1.1. Transverse waves on a string: x Can we use this to describe the matter waves in free space? 2222 Quantum Physics 20067 26 .Rae §2.1 2. t ) wave displacement (in 1d) v wave velocity ( x. B&J §3. t ) e.g. B&M §5.1 An equation for the matter waves: the timedependent Schrődinger equation*** Classical wave equation (in one dimension): 2 1 2 = 2 2 x t2 ( x.
An equation for the matter waves (2) Seem to need an equation that involves the first derivative in time. t = Ae i kx− t d2 d =−k 2 Ae i kx− t . ℏk2 ⇒−i =−k 2 2m 2m ⇒ = iℏ So. wave equation is: 2 2m d d = 2 i ℏ dt dx −ℏ Multiplying both sides by 2m 2 ℏ 2 2 iℏ =− t 2m x 2 (for matter waves in free space) 27 2222 Quantum Physics 20067 . =−i Ae i kx− t 2 dt dx ⇒−i =−k 2 2 ℏ k p2 We want the energy to be ⇒ ℏ = 2m 2m So choose so this is true. but the second derivative in space 2 Try: = t x2 ( x. t ) is "wave function" associated with matter wave Put: x .
t on RHS. need to modify the relationship between energy and momentum: Suggests corresponding modification to Schrődinger equation: p2 E V ( x. ℏ 2 2 iℏ =− V x . t ) 2m Total energy = kinetic energy + potential energy 2 2 d −ℏ d We had: i ℏ = dt 2m dx 2 LHS: Gives ℏ for a plane wave.t 2 t 2m x Timedependent Schrődinger equation Schrődinger 2222 Quantum Physics 20067 28 .t).An equation for the matter waves (3) For particle with potential energy V(x. ℏ k 2 RHS: Gives for a plane wave. 2m ⇒Try adding a term V x .
e. 2222 Quantum Physics 20067 29 . In this form it applies to •A single particle. Therefore its solutions are essentially complex (unlike classical waves.The Schrődinger equation: notes •This was a plausibility argument. where the use of complex numbers is just a mathematical convenience) •Positive i is merely a convention. We believe the Schrődinger equation to be true not because of this argument. that is •Nonrelativistic (i. moving in one direction. •There are limits to its validity. has nonzero rest mass and velocity very much below c) •The Schrődinger equation is a partial differential equation in x and t (like classical wave equation) •The Schrődinger equation contains the complex number i. not a derivation. but because its predictions agree with experiment.
t ≡ H 2 2m d x Potential energy operator 2 2 ] Hence there is an alternative (shorthand) form for timedependent Schrődinger equation: Kinetic energy operator iℏ =H t 2222 Quantum Physics 20067 30 . and usually given the symbol H [ ℏ d − V x . This operator is called the Hamiltonian of the ˆ particle.t t 2m x 2 Can think of the RHS of the Schrődinger equation as a differential operator that represents the energy of the particle.The Hamiltonian operator ℏ 2 2 iℏ =− V x .
as required.t)2 is real.Rae §2. B&J §2. t ∣ dx 2 a b x a b 31 Born 2222 Quantum Physics 20067 . Total probability of finding particle between positions a and b is Ψ2 δx ∑ ∣ x .2 2. hence to square of electromagnetic field strength. Postulate (Born interpretation): probability of finding particle in a small 2 length δx at position x and time t is equal to ( x. t ∣ x 2 x =a b x0 ∫∣ x . B&M §5. so what can be its significance for the results of real physical measurements on a system? Remember photons: number of photons per unit volume is proportional to the electromagnetic energy per unit volume.6) 2 * Note: Ψ(x.1.2.2 The significance of the wave function*** Ψ is a complex quantity. so probability is also real. t ) x (2.
t 2x 0 { (For 0 x0.5001? (b) The probability per unit length of finding the particle at x=0. =1.167 0 0.0 and x=0.5? Total probability =∫∣∣ x 2 0 = ∫ 4x 2 x=0.5 2 (c) The probability of finding the particle between x=0.5 2222 Quantum Physics 20067 32 .Example Suppose that at some instant of time a particle’s wavefunction is x .5 and x=0.5.6? Probability: ∣ ∣ x 2 With: x=0.909 ) (Otherwise) } 2 What is: (a) The probability of finding the particle between x=0.44 0. ⇒ ∣∣ =1 −4 ⇒ Probability =1 x 10 Probability for unit length: ∣∣ = 1.
which can be fixed by imposing the condition (2. multiplied by a constant.E..Normalization Total probability for particle to be anywhere should be one (at any time): ∞ −∞ ∫ ∣ x . Then we can •Calculate the normalization integral •Rescale the wave function as (This works because any solution to the S.7) 2222 Quantum Physics 20067 33 . t N − 1 2 Alternatively: solution to Schrödinger equation contains an arbitrary constant.t ∞ ∞ 2 ∣ ∣ 2 So: ∫ ∣ new∣ x=∫ x −∞ −∞ N N = =1 N x . because the equation is linear and homogeneous) N = ∫ ∣∣ x 2 −∞ ∞ x . t ∣ dx=1 2 Normalization condition Suppose we have a solution to the Schrődinger equation that is not normalized. remains a solution.
in general. t = 4 3 a 2− x 2 34 2222 Quantum Physics 20067 . To get a correctly normalised wavefunction. t ∣ x=∫ x . Therefore is not correctly normalised. equal to 1. t −a a x −∞ ∞ −a = ∫ a − x x= a x− 2 2 2 −a a 2a 3 2a 3 4a 3 = − − = 3 3 3 This is not.example Suppose that at some time we have the following form to the wavefunction: x .Normalizing a wavefunction . t { a 2− x 2 for −a xa 0 otherwise a 2 } 2 Normalisation integral: N = ∫ ∣ x . take: [ x 3 3 a −a ] 3a x .
0 ∫ ∣∣ x∞ −∞ 35 ∞ 2222 Quantum Physics 20067 . Have a finite normalization integral. Be a continuous and singlevalued function of both x and t (in order that the probability density be uniquely defined) Multivalued. B&J §3. x Discontinuous.Rae §2. d Change in only dx allowed if potential ±∞ 2 x 3. Have a continuous first derivative (unless the potential goes to infinity) x Discontinuous.1 2.3 Boundary conditions for the wavefunction Unacceptable The wavefunction must: 1. 2.3.
4 Timeindependent Schrődinger equation*** ℏ Suppose potential V(x.t =− T t 2 V x x T t dt 2m dx Divide by xT t : Equal to constant E as both sides are i ℏ dT ℏ2 d 2 =− V x independent of 2 T dt 2m dx each other. 2 2 i ℏ dT ℏ d =− V x = E 2 T dt 2m dx Independent of 2222 Quantum Physics 20067 time t. B&J §3.e.Rae §2. t= x T t Independent of position x.2.5. Hamiltonian operator does not depend on t) x .3 2. B&M §5. ℏ2 d2 dT i ℏ x .t) (and hence force on 2 2 particle) is independent of time t: iℏ t =− 2m x 2 V x LHS involves only variation of Ψ with t Look for a solution in which the time and space dependence of Ψ are separated: Substitute: RHS involves only variation of Ψ with x (i. 36 .
Timeindependent Schrődinger equation (contd) Solving the time equation: i ℏ dT dT =E ⇒ i ℏ =ET T dt dt Linear ordinary differential equation with constant coefficients. iE i ℏ =E ⇒ =− ℏ Solution is: T t =e The space equation becomes: − iEt ℏ ℏ2 d 2 − V x= E 2m dx2 Now multiply by to get the final version. t Try: T = Ae ⇒ Substitute. ℏ d − V x=E 2 2m d x 2222 Quantum Physics 20067 2 2 or H =E 37 Timeindependent Schrődinger equation .
we will get the same result.t) for the full wavefunction (timedependent Schrődinger equation).t ∣ = e For a stationary state we can use either ψ(x) or Ψ(x. the timeindependent Schrődinger equation is an ordinary differential equation (not a partial differential equation) The sign of i in the time evolution is determined by the choice of the sign of i in the timedependent Schrődinger equation The timeindependent Schrődinger equation can be thought of as an eigenvalue equation for the Hamiltonian operator: Operator × function = number × function ˆ H E (Compare Matrix × vector = number × vector) [See 2246] • • We will consistently use uppercase Ψ(x. 2 ∣ x∣ =∣e ∣ ∣ x ∣ −i E t ℏ 2 −i E t 2 ℏ 2 =∣ x∣ 2 2222 Quantum Physics 20067 38 . and lowercase ψ(x) for the spatial part of the wavefunction when time and space have been separated (timeindependent Schrődinger equation) Probability distribution of particle is now independent of time (“stationary state”): ∣ x .t) to compute probabilities.Notes • • • In one space dimension.
z) [ ] ⇒∣∣2 = Probability per unit volume. B&M §5.6 SE in three dimensions To apply the Schrődinger equation in the real (threedimensional) iℏ =H world we keep the same basic structure: t BUT Wavefunction and potential energy are now functions of three spatial coordinates: Kinetic energy now involves three components of momentum ˆ H E x . t ∣2 V = Probability of finding particle in a small volume dV around (x.t or V r p x 2 p y 2 p z 2 p 2m 2m 2 2 2 2 2 ℏ ℏ − 2 2 =− ∇2 2m x 2 y z 2m 2 ℏ ⇒ − 2m x 2 2 2 Interpretation of wavefunction: ∣ x . t x . tor r . y . z . y. 2222 Quantum Physics 20067 39 . z . B&J §3. y .1. z .1 2. y . y .Rae §3.1. t x x . zor r V x V x .
t ) exp[i (kx t )] plus the energymomentum relationship for freenonrelativistic particles p2 E 2m led us to the freeparticle Schrődinger equation.Puzzle The requirement that a plane wave ( x.) 2222 Quantum Physics 20067 40 . Can you use a similar argument to suggest an equation for free relativistic particles. with energymomentum relationship: E 2 p 2 c 2 m0 2 c 4 Einstein: E =ℏ E =− 2 DeBroglie: p=ℏ k p =− 2 2 t 2 ℏ 2 2 x 2 ℏ 2 ⇒ Try: −ℏ 2 2 t 2 =−ℏ c 2 2 2 x m 0 c 2 2 4 (KleinGordon equation.
1 A Free Particle Free particle: experiences no forces so potential energy independent of position (take as zero) Timeindependent Schrődinger equation: Linear ODE with constant coefficients so try ℏ2 d 2 − =E 2 2m d x exp( x) ℏ2 2 x ℏ2 2 2mE x 2 Substitute: − e =Ee ⇒ − =E ⇒ =− 2 2m 2m ℏ ⇒ Assuming E 0 RHS is ve is imaginary. 2 2 2mE ℏ k =±ik where k 2 = 2 or =E k is DeBroglie wavenumber. B=iC −D 2222 Quantum Physics 20067 41 ikx −ikx .) = C cos kx i sin kxD coskx−i sin kx = A coskxB sin kx where: A=C D . p=ℏ k 2m ℏ General solution: x=Ce De ( C and D are constants.3.
t = x e =Ce De−ikx e = Ce i kx− Et ℏ iEt ℏ ikx i Et ℏ De i kx− Et ℏ Travelling wave moving to the right. t x Travelling wave moving to the left. t −x 2222 Quantum Physics 20067 42 .1 A Free Particle (Cont.3.) Combine with time dependence to get full wave function: x .
since our plausibility argument for the Schrődinger equation was based on this being so) • Note signs: – Sign of time term (iωt) is fixed by sign adopted in timedependent Schrődinger Equation – Sign of position term (±ikx) depends on propagation direction of wave • There is no restriction on the allowed energies. so there is a continuum of states 2222 Quantum Physics 20067 43 .Notes • Plane wave is a solution (just as well.
2mE 2 ℏ a ⇒ x= A cos kxB sin kx With: k 2 = Boundary conditions: Continuity of ψ at x=a: Continuity of ψ at x=a: a=0 ⇒ A cos kaB sin ka=0 −a=0 ⇒ A cos −kaB sin −ka=0 or A cos ka−B sin ka=0 Note discontinuity in dψ/dx allowable.4 3.4. 2222 Quantum Physics 20067 44 .5. since potential is infinite Since: cos−=cos sin −=−sin Even function.Rae §2. B&J §4.2 Infinite Square Well V =∞ Consider a particle confined to a finite length –a<x<a by an infinitely high potential barrier No solution in barrier region (particle would have infinite potential energy). B&M §5. Odd function. In well region: ℏ − =E 2m x 2 2 2 V 0 V(x) V =∞ x a As for free particle.
4. 6..5. x= A cos kx 2a Or. → Same relation between E and k. b) Put A=0 and sin ka=0 n ⇒ ka= n=2.Infinite square well (2) Add and subtract these conditions: Adding gives: 2A cos ka=0 Subtracting gives: 2B sin ka=0 Either. a) Put B=0 and cos ka=0 n ⇒ ka= n=1. ℏ 2 k 2 n2 2 ℏ 2 ⇒ E= = 2m 2m 2a 2 E= n2 2 ℏ 2 8ma 2 2222 Quantum Physics 20067 45 .. x=B sin kx 2a Even solution: ψ(x)=ψ(x) Odd solution: ψ(x)=ψ(x) Energy: Same Schrödinger equation for particle in box as for particle in free space. 7. 2 n ⇒k= ... 2 n ⇒k= . 3..8. .
)⇒sin±2ka=sin ±n =0 a a 2a 2 21 ∫∣∣ x=1⇒ ∫ ∣ A∣ 2 [1cos2kx] x 1 2 2 −a −a ⇒ RHS=∣ A∣ xa ⇒ Choose A so. where a particle is localized in a finite region of space. n k= ( n odd. [ ] Notes on the solution: • Energy quantized to particular values (characteristic of boundstate problems in quantum mechanics..∣ A∣ = a a ∣ A∣2 1 ⇒ x sin 2kx =1 1 A= 2 2k −a a Even soln.Infinite well – normalization and notes Normalization: Need to choose constants so is normalised. stationary state wavefunctions may be even or odd (we say they have even or odd parity) • Compare notation in 1B23 and in books: – 1B23: well extended from x=0 to x=b – Rae and B&J: well extends from x=a to x=+a (as here) – B&M: well extends from x=a/2 to x=+a/2 (with corresponding differences in wavefunction) 2222 Quantum Physics 20067 46 .e: Total over integral is 1). • Potential is even under reflection. (i..
as we will see in §4) State with n = 1 corresponds to a particle bouncing back and forth in the well.The infinite well and the Uncertainty Principle Position uncertainty in well: x≃2a (We know the particle is inside the box. Momentum will be alternately: ℏ ±ℏ k or ± ℏ h ⇒ Momentum uncertainty: p=2 ℏ k = = a 2a Compare with Uncertainty Principle: 2a So: x p=2a h =h 2a 2222 Quantum Physics 20067 Ground state close to minimum uncertanty 47 .) Momentum uncertainty in lowest state from classical argument (agrees with fully quantum mechanical result.
Rae §2.4, B&J §4.6
3.3 Finite square well
V(x) I II V0 x a Region III: III
Now make the potential well more realistic by making the barriers a finite height V0
Assume: 0E V 0
Region I:
ℏ − V 0 =E 2m x 2 x Try: x=e 2 2 ℏ − V 0 =E 2m 2 2 ℏ =V 0− E 0 2m is real. 2m V 0 −E 2 =± = 2 ℏ x − x ⇒=C e D e
2 2
Region II:
a
ℏ 2 2 − =E 2m x 2
Free particle solutions apply:
ℏ2 2 − V 0 =E 2m x 2 x x ⇒ =C ' e D ' e ( same as in Region 1.)
Decaying term forbidden. Growing term allowed.
= A cos kxB sin kx 2mE k 2= 2 ℏ
= D ' e
− x
D is not normalisable so decaying term C is only term allowed. D = 0
2222 Quantum Physics 20067
48
Finite square well (2)
Match value and derivative of wavefunction at region boundaries:
x a
Match ψ: Match dψ/dx:
x a
− a
A cos ka −B sin ka=C e
A coska B sin ka=D e
− a
− a
kA sin ka kB coska = C e
Add and subtract:
−kAsinkakB coska=− D e
− a
2A cos ka =C D e
− a
2Bsinka= D−C e
− a
2 B cos ka=C− De − a 2 Asin ka=C De
2222 Quantum Physics 20067
− a
49
Finite square well (3)
Divide equations:
k tan ka= k cot ka=−k
Must be satisfied simultaneously:
(Unless A=0 and C=−D ) (Unless B=0 and C= D )
Either: k tan ka= and B=0 , C= D (Even solution) Or: k cot ka=− and A=0 , C=−D (Odd solution)
Cannot be solved algebraically. Convenient form for graphical solution:
k & are related by the requirement: ℏ2 2 2 k =V 0 2m 2mV0 2 2 2 2 ⇒ k =k 0 Where: k 0 = ℏ2 Even solution Odd solution
2
k tan ka = k 0 −k
2
⇒ Search for intersections of y=k tan ka or y=k cot ka with a circle y=± k 0 2 −k 2
2222 Quantum Physics 20067 50
k cot ka=− k 0 2 −k 2
k k0=3. a=1 2222 Quantum Physics 20067 51 .Graphical solution for finite well 5 4 3 2 1 0 1 0 2 3 4 5 ktan(ka) sqrt(k0^2k^2) 5 10 kcot(ka) sqrt(k0^2k^2) The radius of the circle corresponds to the depth of the well.
wavefunctions may be even or odd (we say they have even or odd parity) • Limit as V0→∞: k 0 ∞ .) 2 2222 Quantum Physics 20067 52 . circle becomes very large. but there is always at least one (even) state • Potential is even function.Notes • Penetration of particle into “forbidden” region where V>E (particle cannot exist here classically) • Number of bound states depends on depth of potential well. n ⇒ Solutions at ka= (as for an infinite well.
g. solidstate lasers) Kroemer Esaki 53 2222 Quantum Physics 20067 .g. diodes. and whose atomic spacings are so similar that they can be grown together without an appreciable density of defects: Material A (e. GaAs) Position Now used in many electronic devices (some transistors. AlGaAs) Electron potential energy Material B (e.Example: the quantum well Quantum well is a “sandwich” made of two different semiconductors in which the energy of the electrons is different.
so probability of finding it in any finite region is zero 54 Momentum is completely defined 2222 Quantum Physics 20067 . single particle can be anywhere from ∞ to ∞.1.2 3. need to understand normalization of freeparticle planewave solutions.4 Particle Flux −∞ In order to analyse problems involving scattering of free particles.Rae §9. This problem is related to Uncertainty Principle: Position completely undefined. B&M §5.2. ∫ ∣A e ∞ i k x − t 2 ∣ dx= ∫ ∣A∣2 dx=∞ −∞ ∞ Conclude that if we try to normalize so that −∞ ∫ ∣∣ dx =1 2 ∞ will get A=0. B&J §3.
Particle Flux (2) More generally: what is rate of change of probability that a particle exists in some region (say. iℏ =− V ∗ t 2m x 2 ∗ [ [ 2 2 ] ] ] } ] 2222 Quantum Physics 20067 55 . between x=a and x=b)? ∗ dx=∫ ∗ ∫ t a t t a ℏ iℏ =− V 2 t 2m x ⇒∫ a b b b Use timedependent Schrődinger equation: [ ∗ ] a b x dx { [ [ 2 2 ] 1 ∗ ℏ2 2 1 ℏ 2 2 ∗ − V − − V dx iℏ 2m x 2 iℏ 2m x 2 2 1 ℏ2 2 ∗ ∗ = − ∫ x2 − x 2 dx i ℏ 2m a 2 iℏ 2 ∗ ∗ = ∫ x 2 − x 2 dx 2m a b b [ [ ] ℏ .
Particle Flux (3) Integrate by parts: b d iℏ d ∗ ∗ d ∫ dx= 2m dx − dx dt a iℏ d d = ∗ − 2m dx dx [ ∗ b ∗ ] iℏ d ∗ d d d ∗ − ∫ dx dx − dx dx dx 2m a a b ∣ − i ℏ ∗ d − d dx dx ∣ x=b 2m { ∗ } ∣ ∣ x=a Flow of probability leaving at x = b Flow of probability entering at x = a Interpretation: Particle flux at position x : iℏ ∗ x=− − 2m x x ℏ or x = Im ∗ m x [ ∗ [ ] ] Flux entering at x=a Flux leaving at x=b a b x Note: for a stationary state can use either ψ(x) or Ψ(x.t) 2222 Quantum Physics 20067 Note: a wavefunction that is real carries no current 56 .
⇒ x . =−ikA ∗ e−i k x − t x x iℏ x =− [ A∗ e−i k x − t ikA ei k x − t − A ei k x− t −ikA∗ e−i k x − t ] 2m iℏ iℏ 2 =− [2ikAA ∗ ]=− [2ik ∣A∣ ] 2m 2m 2 ∣A∣ ℏ k = m We will use this method. Two common normalising methods: 2 1) One particle per unit length. ⇒ Flux Makes sense: # particles passing x per unit time = # particles per unit length × velocity Wavefunction describes a “beam” of particles. ∣A∣ ℏ k m 2 =1 57 2222 Quantum Physics 20067 . t = A ei k x − t .Particle Flux (4) Sanity check: apply to freeparticle plane wave. ∗ = A ∗ e−i k x− t ∗ =ikA ei k x− t . ⇒∣A∣ =1 2)One particle per unit time.
2 2 Consider a potential which rises suddenly at x=0: Case 1: E<V0 (below step) x<0 (But E > 0 ) Free particle S.3 3.E. 2 2 2 2m x ℏ k =E 2m Choose 1 particle per unit length 2222 Quantum Physics 20067 in incoming beam ⇒ A=1 ℏ ⇒ =Ce De With: =V 0 −E 2m The Ce x term is not normalisable.1.5 Potential Step V(x) Case 1 V0 0 x Boundary condition: particles only incident from left x>0 Same as region 2 of finite well. x − x 2 2 58 .: ℏ 2 2 − =E 2 2m x ⇒ = Ae ikx Be−ikx With: Regions 1 & 3 ℏ − V 0 =E of finite well.Rae §9. B&J §4.
Potential Step (2) Continuity of ψ at x=0: 1 B= D i k 1−B =− D Continuity of d at x 0 : dx Solve for reflection and transmission: i k × equation 1 equation 2: 2 i k =i k − D ⇒ D= 2ik i k − × equation 1 equation 2: i k −i k B=0 ⇒ i k B=− −i k 59 2222 Quantum Physics 20067 .
Transmission and reflection coefficients ℏk m What is the flux reflected back to the left? : ∗ iℏ ∗ − − = B e−i k x 2m x x i ℏ 2 ik x ∣B∣ [ e −i k e −i k x −e i k x i k e i k x ] =− 2m ℏk 2 =− ∣B∣ m Incident particle flux from left= [ ] Transmitted flux: = D e− x iℏ ∣D∣2 [ e− x − e− x −e − x − e − x ] − 2m =0 i.e.: Probability of transmission T =0 Hence the probability of reflection: Reflected flux i k −i k 2 R= =∣B∣ =BB ∗ = =1 Incident flux −i k i k So all particles are reflected. 2222 Quantum Physics 20067 60 .
1 B=F i k 1− B=i k ' F 2 i k =i k k ' F ⇒ k −k ' k k ' k −k ' ⇒ B= k k ' B= i k × equation 1equation 2 ⇒ i k ' × equation 1equation 2 ⇒ i k ' −k i k ' k B=0 Transmission and reflection coefficients: By our argument. reflection probability: k −k ' 2 R=∣B∣ = 2 k k ' 2 No longer 1 if k =k ' 61 2222 Quantum Physics 20067 . x continuous.Potential Step (3) Case 2: E>V0 (above step) Solution for x>0 is now ℏ2 k 2 x= F e G e With: =E −V 0 2m No incoming particles from right ⇒ G=0 ik ' x −i k ' x Matching conditions: continuous.
Summary of transmission through potential step ℏ k ' ℏ k ' 4k2 Transmitted flux: =∣F∣ = m m k k ' 2 Transmitted flux 4k k ' Transmission probability: = = Incident flux k k ' 2 2 Notes: •Some penetration of particles into forbidden region even for energies below step height (case 1. E<V0). E<V0). •No transmitted particle flux. 100% reflection (case 1. 100% transmission for E>V0 2222 Quantum Physics 20067 62 . •Reflection probability does not fall to zero for energies above barrier (case 2. E>V0). with no penetration into barrier. •Contrast classical expectations: 100% reflection for E<V0.
) k −k ' 2 4k k ' k 2 −2 k k 'k ' 2 4 k k ' Check RT = = 2 2 2 k k ' k k ' kk ' =1 as required.Summary of transmission through potential step (Cont. 2222 Quantum Physics 20067 63 .
2222 Quantum Physics 20067 =C e x D e− x x=F e i k x G e−i k x (With k as in region I. ⇒ G=0 64 .5.Rae §2. 1 particle per unit length. B&J §4.e.) ℏ 2 2 With =V 0 −E 2m N.4.6 Rectangular Potential Barrier V(x) Now consider a potential barrier of finite thickness: I V0 x 0 a Boundary condition: particles only incident from left Region II: Region III: II III Assume 0 EV 0 Region I: x= Ae i k x B e−i k x ℏ2 k 2 With =E 2m Take A=1 (i. B&M §5.B: No reason to exclude either solution since region II is finite.) Exclude G term as this term represents particles travelling from the right.9 3.
. 4 i k e−i k a To get F = i k 2 e− a −−i k 2 e a 2222 Quantum Physics 20067 65 ..Rectangular Barrier (2) Match value and derivative of wavefunction at region boundaries: x0 Match ψ: Match dψ/dx: x a [1] [3] C e a D e− a = F e i k a [ 2] [4] C e a − D e− a =i k F e i k a 1 B=C D i k 1− B=C− D Eliminate wavefunction in central region: Eliminate B : i k [1][3]: 2 i k =i k C i k − D a ik a [2][4]: 2 C e =i k F e [2]−[4]: 2 D e− a =−i k F e i k a Eliminate C & D in the same way.
Rectangular Barrier (3) Transmission and reflection coefficients: Transmission probability: 2 2 16 k 2 2 ∣F∣ ∣F∣ T= 2= = 1 ∣i k 2 e− a −−i k 2 e a∣2 ∣A∣ Reflection probability: R=∣B∣ =1−T ⇒ = e a ≫e− a e−2 a −i k 2 e− a 16 k 2 2 2 For very thick or high barrier: a ≫1 T≃ 16 k 2 2 22 ∣−i k ∣ e 2 a = V 02 16 E V 0 −E Nonzero transmission (“tunnelling”) through classically forbidden barrier region: 2222 Quantum Physics 20067 66 .
Field emission of electrons from surfaces (e. Alphadecay and fusion reactors) V V Coulomb interaction (repulsive) Incident particles Strong nuclear force (attractive) Internuclear distance x Distance x of αparticle from nucleus Initial αparticle energy ( Ze) 2 Barrier height ~ ~ MeV 4 0 rnucleus V ? thermal energies (~keV) Work function W Material 3. Nuclear fusion (in stars 2.Examples of tunnelling Tunnelling occurs in many situations in physics and astronomy: 1. in plasma displays) Distance x of electron from surface Vacuum 67 .g.
1 2 x ⇒ ℏ d dx d = = d y d y d x m 0 − 1 2 d dx ℏ m 0 d 2 1 Substitute: − ℏ 0 y 2 = E y 2m ℏ d y 2 2 2 d 2E ⇒ − y 0 =0 = ℏ 0 d y2 2222 Quantum Physics 20067 68 .Rae §2.5.6. B&J §4.7 Simple Harmonic Oscillator Example: particle on a spring. Hooke’s law restoring force with spring constant k: Timeindependent Schrődinger equation: Mass m Force F kx k m Potential energy V ( x ) 1 kx 2 1 m0 2 x 2 2 2 Angular frequency 0 = x ℏ2 d 2 1 − m 0 x 2 =E 2m d x 2 2 m 0 y= ℏ Simplify: change variable to Problem: still a linear differential equation but coefficients are not constant. B&M §5.7 3.
Simple Harmonic Oscillator (2) Asymptotic solution in the limit of very large y: y y= y exp ± 2 n 2 Check: ⇒ 2 2 d y y n−1 n1 =n y exp ± ±y exp ± dy 2 2 2 d y2 n−2 n n2 = [ nn−1 y ±2n−1 y y ] exp ± 2 2 dy y2 n2 2 ≃y exp ± = y (For large y . Only ve part gives normalisable solution.) 2 y Substitute: y= H y exp ± 2 2 S. 69 2222 Quantum Physics 20067 . for large y d2 − y 2 =0 d y2 is satisfied.E.
) H is the correction function to find all solutions.Simple Harmonic Oscillator (2) (Cont.E: 2 y2 y2 2 [ H ' ' y −2 y H ' y y −1 H y ] exp − − y H y exp − = 0 2 2 ⇒ H ' ' y−2 y H ' y−1 H y=0 2222 Quantum Physics 20067 70 . Equation for H: d y2 = [ H ' y− y H y ] exp − dy 2 d2 [ H ' ' y −2 y H ' y − H y y 2 H y ] exp − y 2 d y2 2 Substitute in S.
If n is odd. 2222 Quantum Physics 20067 71 . we must also chose a 0=0 . so all odd terms in the series vanish giving an even solution. We find: •The series for H(y) must terminate in order to obtain a normalisable solution •Can make this happen after n terms for either even or odd terms in series (but not both) by choosing: H y= ∑ a p y p=0 ∞ p 1 2 If n is even.Simple Harmonic Oscillator (3) Must solve this ODE by the powerseries method (Frobenius method). this is done as an example in 2246. so all even terms vanish to give an odd solution. Hn is known as the nth Hermite polynomial.) ⇒ E =ℏ 0 n Label resulting functions of H by the values of n that we choose. =2n1 (For some integer n . we must also choose a1 =0 .
H1 y 2 y. Each H is either an odd or an even function. NOTE: Hn contains yn as the highest power. H 4 y 16 y 4 48 y 2 12. 2222 Quantum Physics 20067 72 . according to whether n is even or odd. first few Hermite polynomials are: H 0 y 1.The Hermite polynomials For reference. H 3 y 8 y 3 12 y. H 2 y 4 y 2 2.
Simple Harmonic Oscillator (4) Transforming back to the original variable x.g. Probability per unit length of finding the particle is: ∣C n x∣ 2 when the system is in state n . 1 x=C 1 x exp ℏ . are normalising constants that satisfy:∫∣ n x∣ d x=1 2 −m 0 x 2 . etc.:∣C 0 x∣ =∣C 0∣ exp ℏ 2222 Quantum Physics 20067 73 . C 1 . the wavefunction becomes: −m0 x 2 0 x=C 0 exp 2ℏ C 0 . etc. 2 2 −m 0 x 2 E.
Simple Harmonic Oscillator (4) (Cont. velocity is given by 1 m v 2V x = E 2 ⇒ pclassical 2 E−V x m 1 1 = E −V x E − 1 m x 2 0 2 ⇒ V= 74 2222 Quantum Physics 20067 .) Compare classical result: probability of finding particle in a length δx is proportional to the time δt spent in that region: p classical x d x dt dx v For a classical particle with total energy E.
Notes
E= n
1 ℏ 0 2
in nth state.
• • • •
“Zeropoint energy”: Ground state energy: E 0 = 1/ 2 ℏ 0 “Quanta” of energy: Can only add or subtract multiples of ℏ 0 Even and odd solutions Applies to any simple harmonic oscillator, including
– Molecular vibrations – Vibrations in a solid (hence phonons) – Electromagnetic field modes (hence photons), even though this field does not obey exactly the same Schrődinger equation
• You will do another, more elegant, solution method (no series or Hermite polynomials!) next year • For highenergy states, probability density peaks at classical turning points (correspondence principle)
2222 Quantum Physics 20067 75
4 Postulates of QM
This section puts quantum mechanics onto a more formal mathematical footing by specifying those postulates of the theory which cannot be derived from classical physics. Main ingredients: 3. The wave function (to represent the state of the system); 4. Hermitian operators (to represent observable quantities); 5. A recipe for identifying the operator associated with a given observable; 6. A description of the measurement process, and for predicting the distribution of outcomes of a measurement; 7. A prescription for evolving the wavefunction in time (the timedependent Schrődinger equation)
2222 Quantum Physics 20067 76
4.1 The wave function
Postulate 4.1: There exists a wavefunction Ψ that is a continuous, squareintegrable, singlevalued function of the coordinates of all the particles and of time, and from which all possible predictions about the physical properties of the system can be obtained. Examples of the meaning of “The coordinates of all the particles”: For a single particle moving in one dimension: x For a single particle moving in three dimensions:
x , y , z
r , ,
etc. etc.
77
For two particles moving in three dimensions: x1 , y1 , z 1 , x2 , y2 , z 2
The modulus squared of Ψ for any value of the coordinates is the probability density (per unit length, or volume) that the system is found with that particular 2222 Quantum Physics 20067 coordinate value (Born interpretation).
78 .1: to each observable quantity is associated a linear. ˆ L1[ f ] ˆ L [f] 2 f 2 xf f df dx NOT linear as Linear as NOT linear as Linear as L1 [c1 f 1 c 2 f 2 ]=c1 f 1 c 2 f 2 2 L 2 [c 1 f 1 c 2 f 2 ]=c 1 x f 1c 2 x f 2 L 3 [c 1 f 1 c 2 f 2 ]= c 1 f 1 c 2 f 2 4 [c 1 f 1 c 2 f 2 ]=c 1 d f 1 c 2 d f 2 L dx dx 2222 Quantum Physics 20067 ˆ L3 [ f ] ˆ L4 [ f ] Note: the operators involved may or may not be differential operators (i. may or may not involve differentiating the wavefunction).e.4.2 Observables and operators Postulate 4. and only if: Examples: which of the operators defined by the following equations are linear? L[c 1 f 1 c 2 f 2 ]=c 1 L[ f 1 ]c 2 L[ f 2 ] For arbitrary functions f 1 & f 2 and constants c 1 & c 2 .2. An operator L is linear if. Hermitian operator (LHO).
Compare the definition of a Hermitian matrix M: M i j =[ M j i ] ∗ Analogous if we identify a matrix element with an integral: M ij −∞ ∫ ∞ f i ∗ O f j dx (see 3226 course for more detail…) 79 2222 Quantum Physics 20067 .g vanishing at infinity.Hermitian operators An operator O is Hermitian if and only if: −∞ ∫ ∞ f ∗ O g dx= [ −∞ ∫ g ∗ O f dx ∞ ] ∗ for all functions f.
(This is 'AntiHermitian.Hermitian operators: examples The operator x is Hermitian −∞ ∫ ∞ f x g dx= ∫ g x f dx= ∗ ∗ −∞ ∞ [ −∞ ∫ g ∗ x f dx ∞ ] ∗ (Since x is real.') ∫ ∞ f ∗ df ∗ =− g dx [ ] d g dx = f 2 dx ∞ −∞ 2 ∫ ∞ [ ∗ dg dx ] ∞ −∞ −∫ ∞ −∞ dg df dx dx dx ∞ ∗ −∞ 2 d2 f ∗ ∗ d f 2 g dx= ∫ g 2 dx dx dx −∞ 2222 Quantum Physics 20067 80 . dx ∞ ∗ [ f ∗ g ]=0 as f & g vanish at ∞ −∞ ∫ g ∗ df dx dx ] ∗ ∴ Not Hermitian because of ve sign.) The operator −∞ ∞ ∫ ∞ =− d2 The operator is Hermitian. 2 dx −∞ [ ∞ dg df ∗ f dx= [ f g ]−∞ − ∫ g dx dx dx −∞ ∗ d is not Hermitian.
2222 Quantum Physics 20067 81 . Compare definition of an eigenvalue of a matrix: M v= n v n Example: the timeindependent Schrődinger equation: H =E The energy in the T. and is an eigenfunction. n is an eigenvalue.Eigenvectors and eigenfunctions Postulate 4.S.I. is an eigenvalue of the Hamiltonian operator. v n is an eigenvector.2.E. Interpretation of Eigenfunction: It is a state of the system in which there is a definite value of the quantity concerned. Definition of an eigenvalue for a general linear operator: Q n=qn n n is an eigenfunction.2: the eigenvalues of the operator represent the possible results of carrying out a measurement of the corresponding quantity. q n is an eigenvalue.
Postulate 4. 2222 Quantum Physics 20067 82 . Start with wavefunction and then measure quantity Q ⇒ Obtain result qm ( one of the eigenvalues of Q ) ⇒ Leave system with corresponding wavefunction m Ensures that we get the same result if we immediately remeasure the same quantity. Proof: Let Q m=q m m Then [ (Where Q is Hermitian.) But −∞ ∫ ∣m∣2 dx is real.2.Important fact: The eigenvalues of a Hermitian operator are real (like the eigenvalues of a Hermitian matrix).) −∞ ∫ m ∗ Q m dx = ∫ m ∗ Q m dx ∞ ⇒ ∞ [ −∞ ∫ m ∞ ][ ∞ −∞ ∗ Q m dx = qm ∫ ∣m∣ dx 2 −∞ ] ∞ ] ∗ (Using f = g = m ) (Which is real. the wavefunction is identical to an eigenfunction of the operator corresponding to the eigenvalue just obtained as the measurement result. ∴ qm is real.3: immediately after making a measurement.
Examples: The Hamiltonian (representing the total energy as a function of the coordinates and momenta) −ℏ 2 2 p2 H= V r = ∇ V r 2m 2m r p L= × =−i ℏ r×∇ or Angular momentum: −ℏ 2 2 V x 2 m x2 ⇒ L =−i ℏ r× ∇ 83 2222 Quantum Physics 20067 .4. x = x (one dimension) x d i.e.3 Identifying the operators Postulate 4.3: the operators representing the position and momentum of a particle are x=x i. p x =−i ℏ dx p x =−i ℏ r =r p =−i ℏ i [ j k =−i ℏ ∇ x y z ] (three dimensions) Other operators may be obtained from the corresponding classical quantities by making these replacements.e.
x de i k x ik x p x e =−i ℏ =−i ℏ i k e dx =ℏ k e i k x e i k x is indeed an eigenfunction of p x with eigenvalue ℏ k This corresponds to a state having a definite momentum ℏ k (in agreement with DeBroglie.Eigenfunctions of momentum The momentum operator is Hermitian. even though isn't.) 2222 Quantum Physics 20067 84 . as required: −∞ ∫ ∞ f ∗ g dx= −i ℏ ∫ f ∗ p = −i ℏ ∫ g ∗ −∞ Its eigenfunctions are plane waves: ik x [ [ ∞ −∞ ∞ ] dg df dx =−i ℏ −∫ g ∗ dx dx dx −∞ df dx = dx ] [ ∗ −∞ g ∗ f dx ∫ p ∞ [ ∞ ] ∗ ] ∗ Factor of −i makes p Hermitian.
∞ −∞ g =m ] ∗ (Since q n is real. taking : ∞ ⇒ RHS= q n ∫ m n dx =q n ∫ m n ∗ dx ∗ [ −∞ ∞ ∫ n∗ Q m dx= ∫ m ∗ Q n dx LHS=q m ∫ n ∗ m dx −∞ −∞ ∞ ] ∗ ∞ [ f = n .) −∞ We chose qm ≠q n ⇒ ∞ −∞ ∫ n∗ m dx=0 ∞ RHS=LHS=q m−qn ∫ n ∗ m dx=0 −∞ 2222 Quantum Physics 20067 85 .Orthogonality of eigenfunctions The eigenfunctions of a Hermitian operator belonging to different eigenvalues are orthogonal. If Proof: Q n=q n n . Q m=qm m with q n≠qm then −∞ ∫ n ∗ m dx=0 ∞ Use Hermitian definition.
Orthonormality of eigenfunctions What if two eigenfunctions have the same eigenvalue? (In this case the eigenvalue is said to be degenerate. We can choose to have all the eigenfunctions orthogonal regardless of whether the eigenvalues are the same or different. 2222 Quantum Physics 20067 −∞ ∫ n∗ m dx= n m 86 . they are said to be orthonormal.) Any linear combination of these eigenfunctions is also an eigenfunction with the same eigenvalue: Q c1 1 c 2 2 =c1 Q 1 c 2 Q 2 =c1 q 1 c 2 q 2 =q c 1 1c 2 2 Q 1 1 =q 1 Q 2 2 =q 2 So we are free to choose as the eigenfunctions two linear combinations that are orthogonal. ∞ If the eigenfunctions are all orthogonal and normalized.
otherwise 0 ∫∣n∣2 dx=1 −a We chose the constants so that normalization is correct: Consider 2 different values n .Orthonormality of eigenfunctions: example Consider the solutions of the timeindependent Schrődinger equation (energy eigenfunctions) for an infinite square well: Eigenfunctions of a H n x 1 cos 2a n= a n x 1 sin 2a a { . for odd n . m : [1] 2 odd values: a a n x m x 1 n ∗ m dx=∫ cos cos dx ∫ a 2a 2a −a −a a nm x n−m x 1 2a 2a = sin sin 2a nm 2a 2a n−m [ nm x n−m x 1 = ∫ cos cos dx 2a −a 2a 2a [ ] ] 2222 Quantum Physics 20067 1 cos cos = [ cos − cos ] 2 a =0 87 −a . for even n } For −a xa .
⇒ ∫ n∗ m dx=n m −a 2222 Quantum Physics 20067 88 .Orthonormality of eigenfunctions: example (Cont.) [2] 2 even values: Similarly =0 sin sin = 1 [ cos −−cos ] 2 [3] Even & odd values: ∫ n∗ m dx=0 −a a a by symmetry.
Complete sets of functions
The eigenfunctions φn of a Hermitian operator form a complete set, meaning that any other function satisfying the same boundary conditions can be expanded as
x = ∑ an n x
n
Where: is an arbitrary function, an are numbers, and n are eigenfunctions.
If the eigenfunctions are chosen to be orthonormal, the coefficients an can be determined as follows:
Consider:
∫ m ∗ dx=∑ an ∫ m ∗ n dx n −∞ −∞ =∑ a n m n
n
∞
∞
⇒
=a m Find number a m , multiply by m ∗ and integrate.
We will see the significance of such expansions when we come to look at the measurement process. 2222 Quantum Physics 20067
89
Normalization and expansions in complete sets
The condition for normalizing the wavefunction is now
1= ∫ ∣ x∣ dx= ∫
2 −∞ ∞
∞
∞
−∞
−∞
∫ m ∗ x n∗ x dx=m n= {1 0
1= ∑ ∑ am a n m n= ∑ ∣a n∣
∗ m n n 2
[∑ am m x ] [ ∑ a n n X ] dx=∑ ∑ am
∗ m n m n
∗
an ∫ m ∗ x n ∗ x dx
−∞
∞
m=n otherwise
}
If the eigenfunctions φn are orthonormal, this becomes
Natural interpretation: the probability of finding the system in the state 2 φn(x) (as opposed to any of the other eigenfunctions) is an
2222 Quantum Physics 20067 90
Expansion in complete sets: example
Consider an infinite square well, with a particle confined to −a xa Hamiltonian has eigenfunctions: n x 1 cos 2a a n x= 1 n x sin 2a a 0
So any function f x satisfying some boundary conditions (i.e zero outside well) can be represented as: nx n x 1 1 f x= ∑ a n cos ∑ sin 2a 2a a n odd n even a Eigenfunctions are orthonormal (see previous working) ⇒ n x 1 cos f x dx ∫ a 2a an = −a a n x 1 sin f x dx ∫ a 2a −a
2222 Quantum Physics 20067
{{
( n odd) ( n even)
otherwise
}
For −a xa
}
This is a Fourier series representation of f x
{
a
( n odd) ( n even)
}
91
the result measuring Q is definitely the corresponding eigenvalue qn. What is the meaning of these “probabilities” in discussing the properties of a single system? Still a matter for debate. but usual interpretation is that the probability of a particular result determines the frequency of occurrence of that result in measurements 2222 Quantum Physics 20067 on an ensemble of similar systems. and that the (normalized) wavefunction can be expanded in terms of the (normalized) eigenfunctions φn of the corresponding operator as x =∑ an n x n Then the probability of obtaining the corresponding eigenvalue qn as the 2 measurement result is an Corollary: if a system is definitely in eigenstate φn.4. 92 .4: suppose a measurement of the quantity Q is made.4 Eigenfunctions and measurement Postulate 4.
p z ] x ⇒ [ x . p x ]=i ℏ But: [ . Note: The commutator of any operator with itself is zero! [ Q . the order in which we allow operators to act on functions matters: Q R ≠ R Q (In general) (In x direction) ⇒ x − =i ℏ p px For example. for position and momentum: [ x . for position and momentum operators: x = x X −i ℏ p d dx d p x =−i ℏ x =−i ℏ x x dx We define the commutator as the difference between the two orderings: So. p y ]=0=[ x .Commutators In general operators do not commute: that is to say. and only if. Q ]= Q Q −Q Q = 0 2222 Quantum Physics 20067 93 . p ]= x − x =i ℏ p p [ Q . R ]=Q R− R Q Two operators commute if. their commutator is zero.
Can also show the converse: any two commuting operators are compatible. Consequence: two compatible observables can have preciselydefined values simultaneously. Commuator here is zero. so no uncertainty.Compatible operators Two observables are compatible if their operators share the same eigenfunctions (but not necessarily the same eigenvalues). definitely obtain result qm once again Compatible operators commute with one another: Consider a general wavefunction Q R = Q ∑ an r n n x n x =∑ a n n x n Expansion in terms of joint eigenfunctions of both operators And: R Q =∑ an r n q n n x n =∑ n an qn r n n x [ ] ⇒ ( r n eigenvalues of R ) ( Using linearity of operator) ⇒ Q R = R Q for any Uncertainty of measurement is proportional to commutator. definitely obtain result rm (the corresponding eigenvalue of R) Wavefunction of system is still corresponding eigenfunction φm Remeasure Q. 2222 Quantum Physics 20067 94 [ Q . Measure observable Q. R ]= 0 . obtain result qm (an eigenvalue of Q) Wavefunction of system is corresponding eigenfunction φm Measure observable R.
x n 1 etc. n 2 etc. Starting at x n . on the x . 'Dirac . consider approximate eigenstates: Suppose we have a series of detectors (in one dimension) each sensitive to the presence of a particle in length Detectors are n .Example: measurement of position Eigenfunctions of position operator x would have to be states of definite position. For now. when x in n region Corresponding eigenfunctions: n x = 0 otherwise x ∞ 2 1 1 Check normalisation: ∫ ∣ n∣ dx = ∫ dx = = 1 ∞ x n { − 1 2 th } n x − − n Check orthogonality: ∫ n m dx =0 ∗ − ∞ Since at least one of n and m is always zero. xn 2222 Quantum Physics 20067 ∞ (If n≠ m ) xn 1 2 1 95 .functions'.axis. n1.
2222 Quantum Physics 20067 96 . (Probability per unit length.Example: measurement of position (2) Now take system with general wavefunction as x =∑ an n x Where: an= ∫ n x x dx = ∫ x dx ∗ − ∞ ∞ Probability that n detector 'fires' =∣a n∣ =∣ x n ∣ ⇒ Consistent with Born interpretation that ∣∣ is a probability density.) th ∞ − ∞ 2 n (Becomes extinct as 0 ) − 1 2 ≃ xn 2 2 − 1 2 Schematically: ≃ x x Measure position ` x n th detector fires.
Expectation values The average (mean) value of measurements of the quantity Q is therefore the sum of the possible measurement results times the corresponding probabilities: 〈 Q 〉 =∑ ∣a n∣ q n 2 n We can also write this as: −∞ ∫ x Q x dx = ∗ ∞ −∞ ∫ ∑ an n x ∑ a m Q m x dx ∗ n m ∗ ∞ ∗ ∞ = ∑ ∑ q m an a m ∫ n m dx n m Since Q m=qm m = ∑ q n∣an∣ n −∞ 2 = 〈Q 〉 −∞ ∫ n ∗ m dx=m n ∞ 2222 Quantum Physics 20067 97 .
homogeneous differential equation.5: Between measurements (i.e. when it is not disturbed by external influences) the wavefunction evolves with time according to the timedependent Schrődinger equation. iℏ =H t Where H is the Hamiltonian operator.) 2222 Quantum Physics 20067 98 . so the linear combination of any two solutions is also a solution: the superposition principle. 1 iℏ = H 1 t iℏ iℏ 2 = H 2 t ⇒ c 1 1 c 2 2= c 1 H 1 c 2 H 2 t = H c 1 1 c 2 2 (Since H is linear.5 Evolution of the system Postulate 4.4. This is a linear.
Calculating time dependence using expansion in energy eigenfunctions Suppose the Hamiltonian is timeindependent. t =exp where the wavefunctions ψ(x) and the energy E correspond to one solution of the timeindependent Schrődinger equation: H n = E n n − i En t ℏ n x We know that all the functions ψn together form a complete set. In that case we know that solutions of the timedependent Schrődinger equation exist in the form: n x . so we can expand x .t = n ∑a e n n − i En t ℏ n x 99 2222 Quantum Physics 20067 . 0=∑ a n n x n Hence we can find the complete time dependence (superposition principle): x . t =∑ a n x .
t = 2 = x x x x 1 2 2 c 2 sin 2 2 cos sin ∣c 1∣ cos 2 a 2a a 2a a Probability distribution in state 1. t=c1 1 x e − i E1t ℏ = Probability density { c 2 2 x e − i E2 t ℏ i E 2−E 1 t ℏ x x − c1 cos c 2 sin e 2a a x . 0=c1 1 xc 2 2 x x x 1 1 =c 1 cos c 2 sin a 2a a a Wave function at a subsequent time t } ∣ ∣ ∣ ∣ ∣∣ [ 1 e a − i E1 t ℏ x . Probability distribution in state 2. { x x 1 c 1 cos c 2 sin e a 2a a − i E 2−E 1 t 2 ℏ ∗ c1 c2 e − i E 2 −E 1 t ℏ ]} 100 Oscillates with an angular frequency: E − E1 = 2 ℏ 2222 Quantum Physics 20067 .Timedependent behaviour: example Suppose the state of a particle in an infinite square well at time t=0 is a `superposition’ of the n=1 and n=2 states x .
101 .Rate of change of expectation value Consider the rate of change of the expectation value of a quantity Q: d 〈Q 〉 d = ∫ ∗ Q dx dt d t −∞ ∞ ∞ ∞ d ∗ dQ d =∫ Q dx∫ ∗ d t dx ∫ ∗ Q d t dx dt −∞ −∞ −∞ ∞ ∞ ∗ 1 = ∫ H Q dx ddQ i1 ∫ ∗ Q H dx t −i ℏ −∞ ℏ −∞ ∞ 〈 〉 H and Q are Hermitian ⇒ ⇒ −∞ ∫ H Q dx= ∫ Q ∞ ∗ ∞ d 〈Q〉 dQ 1 = ∗ Q H − H Q dx ∫ dt dt i ℏ −∞ dQ 1 = 〈[Q . H ]〉 dt iℏ 〈 〉 〈 〉 [ ∞ ∗ −∞ ∗ H dx = ∫ H Q dx −∞ ] ∗ ∞ Comes from intrinsic time dependence of operator. 2222 Quantum Physics 20067 Commutator: Comes from the time dependence of the wave function.
H ] 〉= H − H =0 ∫ ∣∣ dx=constant Total probability conserved (related to existence of a well defined probability flux – see §3.Example 1: Conservation of probability Rate of change of total probability that the particle may be found at any point: t ∣∣ dx= ∫ t −∞ 2 ∞ −∞ ∫ ∗ 1× dx ∞ = 〈 〉 ∞ 2 −∞ 1 1 〈 [1 .4) 2222 Quantum Physics 20067 102 . =0 ⇒ 〈 [ 1 . H ]〉 t iℏ since the commutator of 1 with any operator is zero: Total probability is the “expectation value” of the operator 1.
Even although the energy of a system may be uncertain (in the sense that measurements of the energy made on many copies of the system may be give different results) the average energy is always conserved with time.e. 2222 Quantum Physics 20067 103 . H ]〉 = dt iℏ 〈 〉 dH 0 dt dH If Hamiltonian is constant in time. if =0 dt ⇒ d 〈E 〉 =0 dt Conservation of energy provided Hamiltonian is constant in time.Example 2: Conservation of energy Consider the rate of change of the mean energy: 〈E〉 = ∗ H dx = ∫ t t −∞ ∞ 〈 〉 dH 1 〈 [ H . i.
Reading: Rae Chapter 5.5 5.6.3. In that case it is classically a conserved quantity: dL d = R× p = r × pr × p ˙ ˙ dt dt p = × p r× F =0 m We can write down a quantummechanical operator for it by applying our usual rules: r p L= × =r× −i ℏ ∇ = ∣ i x j y k z −i ℏ d d d −i ℏ −i ℏ dx dy dz ∣ 104 2222 Quantum Physics 20067 .1 Angular momentum operators r F The origin of r is the same central point towards/away from which the force is directed. B&J§§6. B&M§§6.1. Central point Angular momentum is a very important quantity in threedimensional problems involving a central force (one that is always directed towards or away from a central point).26.
5.1 Angular momentum operators (cont.) Individual components: y L x = p z − p y =−i ℏ y z −z z y 105 L y = z p x − p z =−i ℏ z x −x x z L z= x p y − p x =−i ℏ x y −y y x 2222 Quantum Physics 20067 .
p x ] i h [ z . p y ] ih [ L x . pz ] i h [ y. p z ] p x [ . L y ]= L x L y − L y L x = p z− p y p x − x p z − z p x − p z p z − p y y z z x y z = p z p x − p x y p z − p z x p z p z p z − p y z p x z p x p y z p y p z − x p z p y y z z y x y z z x z = p z p x − p x y p z p y x p z− x p z p y y z z z z =−[ . L y ]=i ℏ L z [ L y .5. p z ] x p y z y z =i ℏ p y − p x x y =i ℏ L z By similar arguments get the cyclic permutations: [ L x . L x ]=i ℏ L y 106 2222 Quantum Physics 20067 . L z ]=i ℏ L x [ L z . Remember: [ x.2 Commutation relations*** The different components of angular momentum do not commute with one another.
L z ] = L x [ L x . L z ] L x = L x −i ℏ L y −i ℏ L y L x Important consequence: we cannot find simultaneous eigenfunctions of all three components. L z ] =[ L x 2 . L z ] [ L y 2 . L z ]= [ L x 2 . L z ] =0 and [ L x 2 . L z ]=i ℏ L x L y L y L x ⇒ [ L . L z ] [ L x . L z ] [ L y 2 . But we can find simultaneous eigenfunctions of one component (conventionally the z component) and L2 2222 Quantum Physics 20067 107 . L z ] [ L z . B ] A =−i ℏ L x L y L y L x Similarly: [ L y . but they do commute with the (squared) magnitude of the angular momentum vector: L = Lx L y L z Consider: [ L 2 . B ]= A2 B− A B A A B A− B A2 =a [ A .Commutation relations (2) The different components of L do not commute with one another. B ] [ A . L z ] 2 2 2 2 Note a useful formula: [ A2 .
Spherical polar coordinates are the natural coordinate system in which to operators. In these coordinates. not ˆ r re r r φ x y 0 L=−i ℏ r×∇ =−i ℏ r e r ×∇ =−i ℏ r 1 1 r r r sin 1 Note: Has no e r component L=−i ℏ − e e sin and doesn't depend on r . describe angular momentum. z 1 1 (see 2246) ∇ =e r e e θ r r r sin So the full (vector) angular momentum operator can be written e e 5. note that unit vector k in zdirection satisfies k⋅e=−sin k⋅e=0 ⇒ L z = k⋅L=−i ℏ 108 2222 Quantum Physics 20067 . ∣ r e 0 ∣ k z 2 e To find zcomponent.3 Angular momentum in spherical polar On this slide. hats refer coordinates to unit vectors.
2222 Quantum Physics 20067 1 2 L2 ∇ = 2 r − r ℏ2 r 2 r r 2 . 1 1 2 2 L =−ℏ sin 2 sin sin 2 [ 2 ] 109 Depends only on angular behaviour of wavefunction. 2 1 2 1 1 =−ℏ r 2 r sin −r r r r r 2 sin r 2 sin 2 2 r r r 2 [{ } ] 2 1 2 1 1 2 Since ∇ = 2 r 2 sin 2 2 r r sin r sin 2 r r 2 2 and radial parts of r ∇ and r⋅∇ ∇⋅r cancel. Closely related to angular part of Laplacian (see 2246 and Section 6).L in spherical polar coordinates 2 L 2 = L⋅L=−ℏ 2 r ×∇ ⋅ r×∇ =−ℏ 2 [ r 2 ∇ 2 − r⋅∇ ∇⋅r ] 2 On this slide. not operators. hats refer to unit vectors.
5. ℏ = A e i m 2222 Quantum Physics 20067 i 2 ℏ Quantization of angular momentum about zaxis (compare Bohr model) 110 . =m ℏ where m is an integer.4 Eigenvalues and eigenfunctions Look for simultaneous eigenfunctions of L2 and one component of L (conventional to choose Lz) Eigenvalues and eigenfunctions of L z : −i ℏ = ⇒ = A e i ℏ Note: L z only depends on Physical boundary condition: wavefunction must be singlevalued 2 = Taking our eigenfunction we have: I 2 ℏ i ℏ i 2 ℏ 2 = A e =Ae e e =1 ⇒ =integer .
in the form f .Eigenvalues and eigenfunctions (2) Now look for eigenfunctions of L2.= =e i m Eigenvalue condition becomes (ensures solutions remain eigenfunctions of Lz. as we want) L 2 [ e i m ]= ℏ 2 e i m 2 ei m ei m = ℏ 2 e i m ⇒ −ℏ sin 2 sin sin 2 Divide through by ℏ 2 e i m 1 m2 ⇒ − sin 2 = sin sin [ Let eigenvalue = ℏ 2 2 ] 2222 Quantum Physics 20067 111 .
and sin 2 =1−cos2 =1−2 d m2 2 d 1− − =0 2 d d 1− [ ][ ] This is exactly the Legendre equation.The Legendre equation Make the substitution =cos ⇒ d = =−sin d ⇒ Get: . solved in 2246 using the Frobenius method. 2222 Quantum Physics 20067 112 .
4. P 1 = ¿ 1 P 3 = 5 3−3 2 113 2222 Quantum Physics 20067 .e. (like SHO. 2. 3.1. where l=0.Legendre polynomials and associated Legendre functions In order for solutions to exist that remain finite at μ=±1 (i. . which can be written in terms of the Legendre polynomials: P =1− m l ∣∣ 2 2 d d ∣∣ P l where m is an integer constrained to lie between –l and +l.. where we found restrictions on energy eigenvalue in order to produce normalizable solutions) The finite solutions are then the associated Legendre functions. at θ=0 and θ=π) we require that the eigenvalue satisfies =l l1 . Legendre polynomials: P 0 =1 1 P 2 = 3 2 −1 2 etc..
Spherical harmonics The full eigenfunctions can also be written as spherical harmonics: 2 Y m . m' = 1 ∫ l' 0 0 0 } First few examples (see also 2246): Remember x r sin cos y r sin sin z r cos Y00 ( . they are automatically orthogonal when integrated over all angles (i.l ' m . ) 1 1 1 4 3 3 ( x iy ) sin exp(i ) 8 8 r 3 cos 4 3 z 4 r 3 ( x iy ) 8 r 3 sin exp(i ) 8 114 .=c l m P m cos ei m l l c l m=−1m l−m! 2 l1 lm! 4 { if l=l ' and m=m' otherwise Because they are eigenfunctions of Hermitian operators with different eigenvalues. ) Y10 ( . ) Y11 ( .= l . ] Y m' .e. The constants C are conventionally defined so the spherical harmonics obey the following important normalization condition: ∗ sin d ∫ d [ Y lm . ) Y ( . over the surface of the unit sphere).
Shapes of the spherical harmonics z y x Y 0 0 Y11 Re[Y11 ] Y10 l 1 m0 Yl m l0 m0 Yl m 1 4 l 1 m 1 Yl m 3 sin exp(i ) 8 3 cos 4 Imaginary To read plots: distance from origin corresponds to magnitude (modulus) of plotted quantity.edu/~jws/dpgraph/Yellm.math. (Images from http://odin.html) Real 115 . colour corresponds to phase (argument).nau.
nau. colour corresponds to phase (argument).Shapes of spherical harmonics (2) Y22 z y x Re[Y 2 2 Y21 Re[Y21 ] l2 m 1 Y20 ] l2 m0 Yl m 5 (3cos 2 1) 16 l2 m2 Yl m 15 sin 2 exp(2i ) 32 Imaginary 15 sin cos exp(i ) 8 Yl m To read plots: distance from origin corresponds to magnitude (modulus) of plotted quantity.math.edu/~jws/dpgraph/Yellm. (Images from http://odin.html) Real 116 .
K . with m l . with l 0.5 The vector model for angular momentum*** To summarize: ˆ Eigenvalues of L2 are l (l 1) h 2 . all with the same magnitude and the same zcomponent. since these operators do not commute with Lz.K l m is known as the magnetic quantum number: determines the component of angular momentum along a chosen axis (the zaxis) These states do not correspond to welldefined values of Lx and Ly.5. 0.1. 2. Semiclassical picture: each solution corresponds to a cone of angular momentum vectors.1. 2222 Quantum Physics 20067 117 . 1.K l is known as the principal angular momentum quantum number: determines the magnitude of the angular momentum ˆ Eigenvalues of Lz are mh.
The vector model (2) Lz Example: l=2 ⇒ Eigenvalue of L is l l 1 ℏ =6 ℏ 2 2 2 m=2 L ⇒ Ly L z =2 ℏ Magnitude of angular momentum is m=1 ⇒ L z =ℏ m=0 ⇒ L z =0 m=−1 ⇒ L z =−ℏ l l1 ℏ= 6 ℏ Component of angular momentum in z direction can be Lx m=−2 2ℏ ℏ 0 −ℏ −2 ℏ ⇒ L z =−2 ℏ Reason for restriction on values of m is so L z does not exceed total angular momentum available. 2222 Quantum Physics 20067 118 .
Reading: Rae §3.4.1 The threedimensional square well z Consider a particle which is free to move in three dimensions everywhere within a cubic box. z ) X ( x)Y ( y ) Z ( z ) with boundary conditions 2222 Quantum Physics 20067 a a X ±a=Y ±a=Z ±a=0 119 . y . y. B&J §7. which extends from –a to +a in each direction. or z Separation of variables: take ( x. y x Timeindependent Schrödinger equation within the box is freeparticle like: V(x) − ℏ ∇ 2 x . z =E x .2.11 6. B&M §5. The particle is prevented from leaving the box by infinitely high potential barriers. y . z 2m V V 0 V x. or y.
Threedimensional square well (2) Substitute in Schrödinger equation: ℏ d2 X d2Y d2 Z − YZ Z X X Y =E X Y Z 2 2 2 2m dx dy dz Divide by XYZ: 2 { } ℏ2 1 d 2 X 1 d 2 Y 1 d 2 Z − =E 2 m X d x 2 Y d y2 Z d z2 With E= E x E y E z { } ℏ2 d 2 X − =Ex X 2 m d x2 2 ℏ d2Y − =EyY 2 m d y2 2 ℏ d2 Z − =E z Z 2 m d z2 Three effective onedimensional Schrödinge equations. 2222 Quantum Physics 20067 120 .
Threedimensional square well (3)
Wavefunctions and energy eigenvalues known from solution to onedimensional square well (see §3.2).
8ma Note: We have 3 seperate quantum numbers n x , n y and nz
Total energy is
E x=
n x 2 2 ℏ 2
2
with
n x =1, 2, 3, 4, ...
Similarly for E y and E z
E= E x E y E z 2 ℏ 2 = n x2n y 2n z 2 2 8ma
This is an example of the power of separation of variables in a 3D problem. Now we will use the same technique for the hydrogen atom.
2222 Quantum Physics 20067
121
Reading: Rae §§3.33.4, B&M Chapter 7, B&J §7.2 and §7.5
6.2 The Hamiltonian for a hydrogenic atom*** a e For a hydrogenic atom or ion having nuclear charge +Ze and
single electron, the Hamiltonian is Note spherical symmetry – potential depends only on r Note: for greater accuracy we should use the reduced mass corresponding to the relative motion of the electron and the nucleus (since nucleus does not remain precisely fixed – see 1B2x):
ℏ Z e2 2 H =− ∇ − 2 me 4 0 r
2
r +Ze
me mN = me m N
me = electron mass ,
m N = nuclear mass
The natural coordinate system to use is spherical polar coordinates. In this case the Laplacian operator becomes (see 2246):
1 2 1 1 1 2 L2 ∇ = 2 r sin = 2 r − r r r 2 sin r 2 sin 2 2 r r ℏ2 r 2 r r
2
2
This means that the angular momentum about any axis, and also the total angular momentum, are conserved quantities: they commute with the Hamiltonian, and can have welldefined values in the energy eigenfunctions of the system.
2222 Quantum Physics 20067
d 〈 L2 〉 , L 2 ]=0 ⇔ [H =0 dt d 〈 Lz〉 [ H , L z ]=0 ⇔ d t =0 122
6.3 Separating the variables
Write the timeindependent Schrődinger equation as:
H r , , = E r , , ℏ2 1 d 2 d L2 Z e2 ⇒ − r − = E 2 2 m r2 d r dr 4 0 r 2mr
Now look for solutions in the form
( r , , ) R (r )Y ( , )
Substituting into the Schrődinger equation:
2 ℏ2 1 d 2dR R 2 Ze − Y , 2 r L Y ,− R Y =E R Y 2 2m dr 4 0 r r dr 2mr 2 ℏ 1 d 2 d R Z e2 r 1 L2 2 ⇒ Y ,= E r − − r − Y 2m 2m R d r dr 4 0 LHS depends only on and , RHS depends only on r . Both sides must equal some constant:
[ ]
{
}
2222 Quantum Physics 20067
123
124 . l ⇒ l l 1 ℏ 2 Angular function Y is a spherical harmonic and = 2 me Note: all2222 Quantum Physics for any sphericallysymmetric this would work 20067 potential V(r).The angular equation We recognise that the angular equation is simply the eigenvalue condition for the total angular momentum operator L2: 1 L2 Y = Y 2 me ⇒ L2 Y = 2 m e Y Y is an eigenfunction of operator L 2 This means we already know the corresponding eigenvalues and eigenfunctions (see §5): We know L2 Y m . l = l l 1 ℏ 2 Y m . not just for the Coulomb potential.
but not its orientation.6.4 Solving the radial equation Now the radial part of the Schrődinger equation becomes: − ℏ2 1 d 2dR Z e2 2 r = E r r 2 me R d r dr 4 0 ℏ2 − 1 d 2d R r 2 me r 2 d r dr Note that this depends on l. Define a new unknown function χ by: [ l l 1 ℏ 2 Z e 2 R= E R 2 − 4 0 r 2 me r ] r r d d R 1 d dR ⇒ = − 2 ⇒ r2 = r − dr r dr r dr dr d2 d d d 2d R ⇒ r =r − 2 dr dr dr dr dr 2 ℏ2 d l l 1 ℏ 2 Z e 2 ∴ above becomes: − = E 2 2 − 2m d r 2 me r 4 0 r R r = [ ] 2222 Quantum Physics 20067 125 . but not on m: it therefore involves the magnitude of the angular momentum.
−Z e 4 0 r 2 me V r 2 m e V 2 = 3 r me r 2222 Quantum Physics 20067 126 .The effective potential This corresponds to onedimensional motion with the effective potential Z e 2 l l 1 ℏ 2 V eff r = 4 0 r 2 m e r 2 − V(r) First term: l l1 ℏ 2 me r 2 2 Coulomb attraction: 2 dV −Z e Force F =− = d r 4 0 r 2 Second term: r 'Centrifugal' repulsion: d V l l 1 ℏ 2 Force F = − = dr 2 me r 2 Classically = = L 2 me r 2 2 = L 2I 2 = Rotational kinetic energy.
It makes atomic problems much more straightforward to adopt a system of units in which as many as possible of these constants are one.21159 eV = Hartree. E h 2 4 0 ℏ − − − − In this unit system. a0 2 me e 2 2 me e 18 Unit of energy = = 4. In atomic units we set: Planck constant ℏ = 1(Dimensions [ M L 2 T 1 ]) Electron mass me = 1 (Dimensions [ M ]) e2 3 2 Constant appearing in Coulomb's law = 1 (Dimensions [ M L T ]) 4 0 It follows that: 4 0 ℏ 2 11 Unit of length = = 5.35974 ×10 J = 27. the radial equation becomes 2 1 d l l 1 z − = E 2 − 2 d r2 r 2r [ ] 2222 Quantum Physics 20067 127 .29177×10 m = Bohr radius.Atomic units*** Atomic units: there are a lot of physical constants in these expressions.
so take k = l 1 ⇒ rl 1 as r 0 R rl 128 2222 Quantum Physics 20067 .Solution near the nucleus (small r) For small values of r the second derivative and centrifugal terms dominate over the others. 2 1 d l l 1 − 2 = 0 2 d r2 2r Try a solution to the differential equation in this limit as rk ⇒ ' ' = k k −1 r k− 2 and l l 1 k = l l 1 r 2 r − 2 So: − k k −1l l 1=0 ⇒ k 2 − k − l l 1= 0 ⇒ [ k l ][ k − l 1 ]=0 ⇒ k =−l or k =l 1 We want a solution such that R(r) remains finite as r→0.
F(r): − r r = F r e 2222 Quantum Physics 20067 129 . general solution. We are looking for bound states of the atom. where the electron does not have enough energy to escape to infinity: 2 Put: E =− 2 2 2 1d − =− 2 d r2 2 ⇒ d 2 = − d r2 2 2 2 Solutions: Try =e ⇒ = ⇒ =± r r Take 0 . let us rewrite the solution in terms of yet another unknown function.Asymptotic solution (large r) Now consider the radial equation at very large distances from the nucleus. = A e B e r A e term is not normalisable ∴ A= 0 − x Inspired by this. when both terms in the effective potential can be neglected.
F r = r k ∑ a p r p = ∑ a p r p p p k The indicial equation gives 2222 Quantum Physics 20067 k l or l 1 130 regular solution behaves like F : r l 1 for small r. . using the Frobenius (powerseries) method.Differential equation for F Can obtain a corresponding differential equation for F: d d F r = e − F e r dr dr 2 d d2 F r d F r 2 r = e −2 e F e dr d r2 d r2 Substituting in SE and cancelling factors of E r gives: 1 d2 F dF 1 2 l l 1 Z 1 2 d2 F − − F F =− F ⇒ 2 − 2 2 d r2 dr 2 r 2 2r dr − − − − − − [ ] − l l 1 dF Z F = 2 −2 F 2 dr r r This equation is solved in 2246.
This happens only if Z n where n is an integer l : n l 1. and hence of all atoms) and l (a special feature of the Coulomb potential. It defines the “shell structure” of the 2222 Quantum Physics 20067 atom. 131 . the overall solution behaves like F r ≈ e 2 r ⇒ r ≈ e 2 r e − r = e r (not normalizable) Hence the series must terminate after a finite number of terms. n is known as the principal quantum number. and hence just of hydrogenic atoms). the energy is independent of both m (a feature of all spherically symmetric systems.Properties of the series solution If the full series found in 2246 is allowed to continue up to an arbitrarily large number of terms. l 2K So the energy is E =− 1 2 1 Z =− 2 2 n 2 Note that once we have chosen n.
K 0.2.K (l 1). (l 1).….… we have a definite energy: Z2 En 2 (in atomic units) 2n − 1 16 0 − 1 9 Z E in units E 2 h 2 all x7 − 1 4 all x3 all x5 For each value of n.5 The hydrogen energy spectrum and wavefunctions*** Each solution of the timeindependent Schrődinger equation is defined by the three quantum numbers n. l = 0 132 .h.6.l.i… etc) n− 1 l =0 ∑ 2 l 1 = n 2 2222 Quantum Physics 20067 2p 3s ⇒ ⇒ n = 2 .1. we can have n possible values of the total angular momentum quantum number l: l=0. l =1 n =3 .2.n1 For each value of l and n we can have 2l+1 values of the magnetic quantum number m: 1 l=0 l=1 l=2 l=3 Traditional nomenclature: l=0: s states (from “sharp” spectral lines) l=1: p states (“principal”) m l .m For each value of n=1. l l=2: d states (“diffuse”) The total number of states (statistical weight) associated l=3: f states (“fine”) with a given energy En is therefore …and so on alphabetically (g.
= Rn l r Y m . ∣ =1 2 2 m 0 ∞ But: ∫ sin d ∫ d ∣Y lm . 0 0 ∞ 2 2 3 2 1− −Z r 2 a0 ⇒ ∫ r R n l r dr =1 0 2 2 Zr 3a e a0 Zr 6 a0 2 −Z r 0 Note: −Z r 3 a0 Probability of finding electron between radius r and r+dr is: 1− Zr e a0 2 2 r 2 Rn l 2 r =n l r since: n l = r R n l r 2Z r 2Z r 3a 1− e 3 a 0 27 a 02 −Z r 0 Only s states (l=0) are finite at the origin. l Normalization chosen so that: 0 2 0 2 1 Z R 21 r = 3 2 a0 R 20 r =2 Z 2 a0 4 Z R32 r = 27 10 3 a 0 R31 r = 4 2 Z 9 3 a0 3 2 3 2 Z R30 r =2 3 a0 3 2 e −Z r a0 3 2 Z r 2a e a0 Zr e 2 a0 3 2 −Z r 0 ∫ r R n l r dr ∫ sin d ∫ d ∣Y l .e. Radial functions have (nl1) zeros. NOT the probability per unit volume of 2 finding the particle at a given point in space: ∣n l m∣ 2222 Quantum Physics 20067 133 . . ∣ =1 for spherical harmonics. r 2 R n l r is the probability per unit length of finding the electron at a radius r .The radial wavefunctions Radial wavefunctions Rnl depend on principal quantum number n and angular momentum quantum number l (but not on m) Z R10 r =2 a0 Full wavefunctions are: n l m r . i.
m l .3.K Electron otherwise moves according to classical mechanics and has a single welldefined orbit with radius n 2 a0 rn . Eh Hartree 2n Z2 En 2 Eh . l Electron wavefunction spread over all radii. n 1.Comparison with Bohr model*** Bohr model Angular momentum (about any axis) assumed to be quantized in units of Planck’s constant: Quantum mechanics Angular momentum (about any axis) shown to be quantized in units of Planck’s constant: Lz nh. not by angular momentum: 1 Z2 En 2 Eh .K . but is determined solely by principal quantum number. Can show that the quantum mechanical expectation value of the quantity 1/r satisfies Z . 2. a0 Bohr radius r n 2 a0 Energy quantized. a0 Bohr radius Z Energy quantized and determined solely by angular momentum: Lz mh. Eh Hartree 2n 2222 Quantum Physics 20067 134 .
2222 Quantum Physics 20067 135 . and in particular to a small “Lamb shift” of the energy levels. Including these effects gives rise to • “fine structure” (from the interaction of the electron’s orbital motion with its spin).6 The remaining approximations • This is still not an exact treatment of a real H atom. and • “hyperfine structure” (from the interaction of the electron’s spin with the spin of the nucleus) – We have neglected the fact that the electromagnetic field acting between the nucleus and the electron is itself a quantum object. – We have neglected the motion of the nucleus. – We have used a nonrelativistic treatment of the electron and in particular have neglected its spin (see §7). This leads to “quantum electrodynamic” corrections.6. because we have made several approximations. To fix this we would need to replace me by the reduced mass μ (see slide 1).
Reading: Rae Chapter 6. B&M Chapter 8 (all go further than 2B22) 7. classical interaction energy is: E =− ⋅B = B L ℏ ⋅ B Corresponding quantum mechanical expression (to a good approximation) involves the angular momentum operator: Contribution to Hamiltonian involving B = H = B ℏ L ⋅ B 136 2222 Quantum Physics 20067 .8. B&J §6.1 Atoms in magnetic fields Orbit behaves like a current loop: μ r v Interaction of classically orbiting electron with magnetic field: ev ( ve sign because chage =− e ) 2 r Magnetic moment = current × area −e v −e L = r 2= me v r =− B 2 me ℏ 2r eℏ Where B = (The Bohr magneton) 2 me Loop current = − In the presence of a magnetic field B.
B ˆ ˆ ˆ H H 0 B z Lz h ˆ H 0 m E0 m . The Hamiltonian operator is We chose energy eigenfunctions of the original atom that are eigenfunctions of Lz so these same states are also eigenfunctions of the new H.Splitting of atomic energy levels Suppose field is in the z direction. z m m ⇒ m = H 0 m B B z L z m H ℏ = E 0m B B z m New eigenvalue. 2222 Quantum Physics 20067 137 . ˆ L mh .
Splitting of atomic energy levels (2) B0 B 0 m= l E=E0 (2l+1) states with same energy: m=l. l=0. n=1. 138 . An s state (such as the ground state of 2222 Quantum Physics 20067 hydrogen.…+l E = E 0 l B B z m= l −1 m=−l E = E 0− l B B z (Hence the name “magnetic quantum number” for m. m=0) should not be split.) Predictions: should always get an odd number of levels.
with magnetic moments = ± B Consistent neither with classical physics (which would predict a continuous distribution of μ) nor with our quantum mechanics so far (which always predicts an odd number of groups. S Results show two groups of atoms. Gerlach 139 . hydrogen. and just one 2222 Quantum Physics 20067 for an s state).7. sodium) Study deflection of atoms in inhomogeneous magnetic field. the atom is pushed towards high fields.g.2 The SternGerlach experiment*** Produce a beam of atoms with a single electron in an s state (e. If is antialigned with B atom is pushed towards low fields. deflected in opposite directions. Force on atoms is N F =∇ ⋅ B ⇒ if is aligned with B .
3 The concept of spin*** Try to understand these results by analogy with what we know about the ordinary (“orbital”) angular momentum: must be due to some additional source of angular momentum that does not require motion of the electron. Known as “spin”. but can be an integer or half integer and m s can vary from S to − S Goudsmit Uhlenbeck in integer steps. S y ]= i ℏ S z etc. Where S x . Introduce new operators to represent spin. Pauli 140 . S z are components of spin angular momentum. assumed to have same commutation relations as ordinary angular momentum: [ S x . S y .7. Define: S 2= S x 2 S y 2 S z 2 Corresponding eigenfunctions and eigenvalues: S 2 = s = s s 1 ℏ 2 s m m S z s = m s ℏ s ms s s ms ms = magnetic spin quantity (will see in Y3 that these equations can be derived directly from the commutation relations) Find S does not have to be an integer.
.Spin quantum numbers for an electron From the SternGerlach experiment.....00231930437 (Quantum Electrodynamics) g = g factor (Measures how effective this particular form of angular momentum is at producing a magnetic moment. have H H0 =± 2 ms B General interaction with magnetic field: = B ℏ B ⋅ L ⋅ g S Spin angular momentum is twice as “effective” at producing magnetic moment as orbital angular momentum. So. g = 2 (Dirac's relativistic theory) g = 2.) 2222 Quantum Physics 20067 141 . we know that electron spin along a given axis has two possible values.. s −± 1 2 But we also know from SternGerlach that magnetic moments associated with the two possibilities are = ± B So. choose S= 1 2 ⇒ m s=− s....
. 2 Note that the spin functions χ do not depend on the electron coordinates r. = R n . S m s ms i. s .θ. they represent a purely internal degree of freedom. and field in the z direction: Lz g S z ℏ Change in energy is B B z m g m s ≃ B B z m 2 m s H = H0 B B z ⇒ For ground state l =0. 2 states. l .φ. get E =± B B z as observed.e.m. 142 2222 Quantum Physics 20067 . m=0 .s.ms.l. m r . with spin included. with m s=± 1 for each one we found before. H atom in magnetic field. Corresponding to a full wavefunction n . m .A complete set of quantum numbers Hence the complete set of quantum numbers for the electron in the H atom is: n. l r Y l .
g. use the vector model once again: Vector addition between orbital angular momentum L (of magnitude L) and spin S (of magnitude S): produces a resulting angular momentum vector J: quantum mechanics says its magnitude lies somewhere between LS and L+S. l 1 Determines length of resultant 2 2 angular momentum vector m j j .4 Combining different angular momenta So. an electron in an atom has two sources of angular momentum: •Orbital angular momentum (arising from its motion through the atom) •Spin angular momentum (an internal property of its own). . j Determines orientation Eigenvalues of J = j j 1 ℏ 2 Eigenvalue of J z = m j ℏ S J LS L Lz S m j =3/ 2 LS Ly m j =1/2 L m j =−1/ 2 L+S 3 1 j= . To think about the total angular momentum produced by combining the two.7.K .(in integer steps). 2 2 Lx m j =−3/ 2 143 e. corresponding `total angular momentum’ quantum numbers are j l 1 . For a single electron. l =1 .
and a quartet of states adding 4 different values of m j Even in no B . m j =± The 2p state: n= 2 . 2 2 . S = 1 2 1 . 2 3 2 Get a doublet of states adding 2 different values of m j .field. s= 1 2 ⇒ 1 possibility j = 1 2 1 2 Purely spin angular momentum. 2 1 . 2 − 3 . Now 2 possibilities: j = ⇒ m j= − 1 . j = (Fine structure effects. l =1 . 2 1 .) 2222 Quantum Physics 20067 144 1 3 and j = states have different energies.Example: the 1s and 2p states of hydrogen The 1s state: l =0 . 2 3 2 . 2 − 1 .
from whatever source. s2 1 2 Then construct combined spin S of both electrons: L must be between ∣L1− L 2∣=1 and L 1 L 2= 1 ⇒ S =0 . 1 ∣S 1 S 2∣=0 and S 1 S 2 =1 Hence there are two possible terms (combinations of L and S): …and four levels (possible ways of combining L and S to get different total angular momentum quantum numbers) ⇒ S =0 . s1 1 . 2 145 2222 Quantum Physics 20067 . 2 l2 1. one in 1s state and one in 2p state (defines what is called the 1s2p configuration in atomic spectroscopy): First construct combined orbital angular momentum L of both electrons: l1 0. 1 L= 1 . L= 1 . S =0 S =1 ⇒ ⇒ J =1 J =0 . For example for two electrons in an excited state of He atom.Combining angular momenta (2) The same rules apply to combining other angular momenta.1 .
L= 1 . (Singlet) 3 P1 . 3 P2 146 2222 Quantum Physics 20067 .Term notation Spectroscopists use a special notation to describe terms and levels: 2 S 1 LJ •The first (upper) symbol is a number giving the number of spin states corresponding to the total spin S of the electrons •The second (main) symbol is a letter encoding the total orbital angular momentum L of the electrons: •S denotes L=0 •P denotes L=1 •D denotes L=2 (and so on). Example: terms and levels from previous page would be: L= 1 . •The final (lower) symbol gives the total angular momentum J obtained from combining the two. S =0 S =1 ⇒ ⇒ 1 P1 3 P0 .
x0 2 x Can also write this as a Fourier transform (see 2246): ∞ 1 ∫ x = k e i k x dk 2 ∞ − (expansion in eigenstates of momentum) 2222 Quantum Physics 20067 147 k .5 Wavepackets and the Uncertainty Principle revisited (belongs in §4 – nonexaminable) Can think of the Uncertainty Principle as arising from the structure of wavepackets. Consider a normalized wavefunction for a particle located somewhere near (but not exactly at) position x0 x = 2 2 − 1 4 exp [ − − x x 0 4 2 2 ] 2 ( x) 2 Probability density: ∣ x ∣ = 2 2 − 1 2 exp [ 2 − − 0 2 x x 2 ] % (k ) = standard deviation.7.
5 Wavepackets and the Uncertainty Principle revisited (belongs in §4 – nonexaminable) (cont.) Compare x =∑ an n x ∞ 1 ∫ then k = x e i k x dx 2 ∞ − − Compare an = ∫ x x dx ∗ − ∞ ∞ ei k x k ⇒ n x (Eigenfunction) (Expansion coefficient) 2222 Quantum Physics 20067 148 .7.
dx ' =dx = 2 2 ∣k ∣ = ∫ ∣k ∣2 dk = ∞ 2 −∞ [ −1 4 exp [−i k x 0 ] exp [ −k 2 2 ] − 1 2 2 2 exp −2 k − 1 2 2 2 ] ∫ exp − 2 2 2 2 =1 ∞ ∞ [ ] 2 − x 2 dx = a a .Fourier transform of a Gaussian 1 k = ∫ x exp [−i k x ] dx 2 −∞ 1 ∞ ∞ − x− x 0 1 = exp [−i k x ] dx 2 2 4 ∫ exp − 2 4 2 −∞ 1 ∞ 2 − x− x 0 1 = −i k x − x0 dx 2 2 4 exp [ −i k x0 ] ∫ exp − 2 2 4 −∞ 1 ∞ 2 2 [ 2 − [ x− x 0 2 i k ] 1 2 2 = −k dx 2 2 4 exp [ −i k x0 ] ∫ exp − 2 4 2 −∞ − 1 2 = 2 4 exp [ −i k x0 ] exp [−k 2 2 ] ∫ exp − x ' 2 dx 4 2 −∞ − 1 2 = 2 4 exp [ −i k x0 ] exp [−k 2 2 ] 2 2 1 1 ∞ ] [ [ ] [ 2 ] ] With: x '= x − x 02 i k 2 . ∫ x exp − ∞ 2 ∞ [ ] 2 − a x dx = 2 a2 149 3 2222 Quantum Physics 20067 .
so: ℏ2 2 2 2 x p = = 2 4 4 ℏ x p 2 ℏ2 Rigorous statement of uncertainty principle for position and momentum. 150 2222 Quantum Physics 20067 . can show that this form of wavepacket (“Gaussian wavepacket”) minimizes the product of Δx and Δp.Wavepackets and Uncertainty Principle (2) Meansquared uncertainty in postion x 2 = x−x 2 = 0 〈 〉 −∞ x−x 0 ∣ x ∣ dx= 2 ∫ 2 2 ∞ Mean momentum: p=ℏ k ∣ k ∣ is symmetric about k =0 2 2 2 2 2 ⇒ 〈 p 〉 =0 Meansquared uncertainty in momentum: p = 〈 p 〉 =ℏ 〈 k 〉 = ℏ2 4 2 ⇒ In fact.
R 1 q r ∣〈 [ Q . R ] 〉∣ 2 Where: q and r are RMS uncertainties in Q and R 2222 Quantum Physics 20067 151 . General result (see third year. or Rae §4. so they cannot simultaneously have precisely defined values.Wavepackets and Uncertainty Principle (3) Summary Three ways of thinking of Uncertainty principle: (3) Arising from the physics of the interaction of different types of measurement apparatus with the system (e. (5) Arising from the fact that x and p are not compatible quantities (do not commute). in the gammaray microscope).5): For general noncommuting operators Q . (4) Arising from the properties of Fourier transforms (narrower wavepackets need a wider range of wavenumbers in their Fourier transforms).g.
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