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© J Kiefer 2006
Table of Contents
TABLE OF CONTENTS .............................................................................................................. 1
I. RELATIVITY ............................................................................................................................. 2
A. Frames of Reference ................................................................................................................................................ 2
B. Special Relativity ...................................................................................................................................................... 5
C. Consequences of the Principle of Special Relativity ............................................................................................. 8
D. Energy and Momentum ......................................................................................................................................... 14
E. A Hint of General Relativity .................................................................................................................................. 19
II. QUANTUM THEORY ........................................................................................................... 21
A. Black Body Radiation ............................................................................................................................................ 21
B. Photons .................................................................................................................................................................... 27
C. Matter Waves ......................................................................................................................................................... 31
D. Atoms ....................................................................................................................................................................... 38
III. QUANTUM MECHANICS & ATOMIC STRUCTURE (ABBREVIATED) ................. 46
A. Schrödinger Wave Equation—One Dimensional ................................................................................................ 46
B. OneDimensional Potentials .................................................................................................................................. 48
D. The Hydrogen Atom .............................................................................................................................................. 54
E. Multielectron Atoms ............................................................................................................................................. 61
1
I. Relativity
A. Frames of Reference
Physical systems are always observed from some point of view. That is, the displacement,
velocity, and acceleration of a particle are measured relative to some selected origin and
coordinate axes. If a different origin and/or set of axes is used, then different numerical values
are obtained for r
, v
, and a
, even though the physical event is the same. An event is a
physical phenomenon which occurs at a specified point in space and time.
1. Inertial Frames of Reference
a. Definition
An inertial frame is one in which Newton’s “Laws” of Motion are valid. Moreover, any frame
moving with constant velocity with respect to an inertial frame is also an inertial frame of
reference. While r
and v
would have different numerical values as measured in the two
frames, a m F
· in both frames.
b. Newtonian relativity
Quote: The Laws of Mechanics are the same in all inertial reference frames. What does “the
same” mean? It means that the equations and formulae have identical forms, while the numerical
values of the variables may differ between two inertial frames.
c. Fundamental frame
It follows that there is no preferred frame of reference—none is more fundamental than another.
2. Transformations Between Inertial Frames
a. Two inertial frames
Consider two reference frames—one attached to a cart which rolls along the ground. Observers
on the ground and on the cart observe the motion of an object of mass m.
The S’frame is moving with velocity v
relative to the Sframe. As observed in the two frames:
2
In S’ we’d measure ∆ t’, ∆ x’, and
t
x
u
x
′ ∆
′ ∆
·
′
.
In S we’d measure ∆ t, ∆ x, and
t
x
u
x
∆
∆
·
.
b. Galilean transformation
Implicitly, we assume that t t ′ ∆ · ∆ . Also, we assume that the origins coincide at t = 0. Then
t v x x
x
′ ∆ + ′ ·
t v y y
y
′ ∆ + ′ ·
t v z z
z
′ ∆ + ′ ·
t t ′ ∆ · ∆
The corresponding velocity transformations are
x x x x
v u v
dt
x d
dt
dx
u +
′
· +
′
· ·
y y y y
v u v
dt
y d
dt
dy
u +
′
· +
′
· ·
z z z z
v u v
dt
z d
dt
dz
u +
′
· +
′
· ·
For acceleration
dt
dv
a
dt
du
a
x
x
x
x
+
′
· ·
dt
dv
a
dt
du
a
y
y
y
y
+
′
· ·
dt
dv
a
dt
du
a
z
z
z
z
+
′
· ·
Note that for two inertial frames, the
′
·
x x
a a ,
′
·
y y
a a , and
′
·
z z
a a
.
3
Example
Sframe
dt
p d
dt
u d
m a m F
· · ·
, if m is constant.
S’frame
dt
p d
a m F
′
· ′ · ′
, where
u m p ′ · ′
. But v u u
− · ′ , so
F
dt
u d
m
dt
v d
dt
u d
m F
· ·
,
`
.

− · ′
. That is,
a a ′ ·
, as they must for 2 inertial reference frames.
Notice the technique. Write the 2
nd
“Law” in the S’frame, then transform the position and
velocity vectors to the Sframe.
4
B. Special Relativity
1. MichelsonMorley
a. Wave speeds
Midway through the 19
th
century, it was established that light is an electromagnetic (EM) wave.
Maxwell showed that these waves propagate through the vacuum with a speed
8
10 3x c ≈ m/sec.
Now, wave motion was well understood, so it was expected that light waves would behave
exactly as sound waves do. Particularly the measured wave speed was expected to depend on the
frame of reference.
In the Sframe, the speed of sound is u
; in the S’frame the speed is u′
. The source and the
medium are at rest in the Sframe. We find (measure) that v u u
+ ′ · , in conformity with
Newtonian or Galilean relativity. We may identify a “preferred” reference frame, the frame in
which the medium is at rest.
b. MichelsonMorley
Throughout the latter portion of the 19
th
century, experiments were performed to identify that
preferred reference frame for light waves. The questions were, what is the medium in which
light waves travel and in what reference frame is that medium at rest? That hypothetical medium
was given the name luminiferous ether (æther). As a medium for wave propagation, the ether
must be very stiff, yet offer no apparent resistance to motion of material objects through it.
The classic experiment to detect the
ether is the MichelsonMorley
experiment. It uses interference to show
a phase shift between light waves
propagating the same distance but in
different directions.
The whole apparatus (and the Earth) is
presumed to be traveling through the
ether with velocity, v
. A light beam
from the source is split into two beams
which reflect from the mirrors and are
recombined at the beam splitter—
5
forming an interference pattern which is projected on the screen. Take a look at the two light
rays as observed in the ether rest frame.
The sideward ray:
The time required for the light ray to travel
from the splitter to the mirror is obtained
from
2
1
2
2
2 2 2
1 ) ( ) (
−
,
`
.

− · ⇒ + ·
c
v
c
t vt ct
.
Now c >> v, so use the binomial theorem
to simplify
,
`
.

+ ≈
2
2
2
1
1
c
v
c
t
.
The total time to return to the splitter is twice this:
,
`
.

+ ≈ ·
2
2
1
2
1
1
2
2
c
v
c
t t
.
For the forward light ray, the elapsed time from splitter to mirror to splitter is
. 1
2
1
2
2
2
2
2
2
,
`
.

+ ≈
,
`
.

− ·
+
+
−
·
c
v
c c
v
c v c v c
t
The two light rays recombine at the beam splitter with a phase difference [let
c
λ
τ ·
.]:
( )
2
2
2
2
1 2
2
1 2
c
v c
c
v
c
t t
c t
λ λ λ τ
· · − ·
∆
.
Since
0 ≠
∆
τ
t
, the two light rays are out of phase even though they have traveled the same
distance. By measuring t ∆ one could evaluate v .
However, no such phase difference was/is observed! So, there is no ether, no v
with respect to
such an ether. This null result is obtained no matter which way the apparatus is turned. The
conclusion must be that either the “Laws” of electromagnetism do not obey a Newtonian
relativity principle or that there is no universal, preferred, rest frame for the propagation of light
waves.
c. Expedients to explain the null result
length contraction—movement through the ether causes the lengths of objects to be shortened in
the direction of motion.
etherdrag theory—ether is dragged along with the Earth, so that near the Earth’s surface the
ether is at rest relative to the Earth.
6
( ) +
+
+ + · −
− 2
! 2
) 1 (
1 1 x
n n
nx x
n
Ultimately, the expedients were rejected as being too ad hoc; it’s simpler to say there is no ether.
This still implies that the “Laws” of electromagnetism behave differently under a transformation
from one reference frame to another than do the “Laws” of mechanics.
2. Postulates of Special Relativity
a. Principle of Special Relativity
It doesn’t seem sensible that one “part” of Physics should be different from another “part” of
Physics. Let’s assume that they are not different, and work out the consequences. This is what
Einstein did. He postulated that ‘All the “Laws” of Physics are the same in all inertial reference
frames.’
b. Second Postulate
The second postulate follows from the first. ‘The speed of light in a vacuum is (measured to be)
the same in all inertial reference frames.’
When the speed of light is measured in the two reference frames, it is found that v c c + ′ ≠ ,
rather c c ′ · . Evidently, the Galilean Transformation is not correct, or anyway not exact. In any
case, we assume the postulates are true, and work out the consequences.
7
C. Consequences of the Principle of Special Relativity
1. Time Dilation
a. Events
An event may be regarded as a single observation made at a specific location and time. One
might say that an event is a point in spacetime (x,y,z,t). Two events may be separated by
intervals in either space or in time or in both.
b. Time intervals
Consider a kind of clock:
We observe two events: i) the emission of a flash at O’ and ii) the
reception of the flash at O’. In this case,
0 · ′ ∆ · ′ ∆ · ′ ∆ z y x
. The
time interval between the two events is
c
d
t
′
· ′ ∆
2
.
Now let’s view the same two events from the point of view of
another frame, S. As shown below, the S’frame is moving to the
right with speed v relative to the Sframe. In the Sframe, 0 ≠ ∆x .
The elapsed time is
c
d
t
2
· ∆
, where
2 2 2
+
′
· d d
. Substitute for d ,
d′ , and in terms of t ∆ , t′ ∆ , c, and v.
4 4 4
2 2 2 2 2 2
t v t c t c ∆
+
′
∆
·
∆
Solve for
2
2
2
1
2 2
2
1
c
v
t
v c
c
t t
−
′ ∆
·
,
`
.

−
′ ∆ · ∆
.
8
example (prob. 111 in the text)
The lifetime of a pion in its own rest frame is
8
10 6 . 2
−
· ′ ∆ x t sec. Consider a pion moving with
speed c v 95 . 0 · in a lab—what will be measured as its lifetime in the lab?
sec 10 33 . 8
312 . 0
sec 10 6 . 2
95 . 0 1
sec 10 6 . 2
1
8
8
2
8
2
2
−
− −
· ·
−
·
−
′ ∆
· ∆ x
x x
c
v
t
t
.
The lifetime of a fastmoving particle is measured by noting how far it travels before decaying.
In this example 7 . 23 sec 10 33 . 8 95 . 0
8
· ⋅ · ∆ ·
−
x c t v m. In practice, we measure and
compute t ∆ .
c. Proper time
The proper time is the time interval measured by an observer for whom the two events occur at
the same place, so that
0 · ′ ∆ · ′ ∆ · ′ ∆ z y x
.
2. Length Contraction
a. “Contraction”
Consider an object, such as a meter stick, of length L in its
own rest frame, S.
A second frame, S’, moves to the right
with a speed v relative to S.
We observe two events:
i) the point A passes the left end of
the stick
ii) the point A passes the right end of
the stick.
9
As measured in the S’ frame, t v L ′ ∆ · ′ and 0 · ′ ∆x .
In the S frame, L x · ∆ and
2
2
1
c
v
t
t
−
′ ∆
· ∆
. Therefore,
2
2
2
2
1 1
c
v
L
c
v
t v L − · − ∆ · ′ .
An observer in the S’ frame observes the stick to be shorter (contracted) than does the observer
in the S frame. Notice particularly that the stick is at rest in the S frame.
The contraction takes place in the direction of the relative motion. Lengths perpendicular to v
are not affected. So for instance in the situation discussed above the width and thickness of the
meter stick are still measured the same in both reference frames.
b. Proper length
The proper length of an object is that length measured in the rest frame of the object.
3. Simultaneity
a. Spacetime
Each event has associated with it four numbers: x, y, z coordinates and a “value of time” which
we read off a clock located at that spatial location. There is no central universal clock, rather
there is a clock at every point in space.
b. Synchronization
We would like all clocks in a reference frame to display exactly the same reading
simultaneously, but can this be arranged? Only by the exchange of signals, which is another way
of saying only in terms of intervals. However, as we have seen, intervals are not the same for
observers in different inertial reference frames. Therefore, the concept of two events being
simultaneous has no absolute meaning.
c. Nonsimultaneity
Two events viewed as simultaneous in one frame will not be seen as occurring simultaneously in
another frame.
example: a train moving with constant velocity on a straight, smooth track. One observer rides
on the train, the other observer stands beside the track.
Flashes of light are emitted at the points C
1
and C
2
when the origins (O & O’) of the two frames
coincide. To the trackside observer at O, the flashes are simultaneous. To the observer on the
train, however, the flash emitted at C’
2
is received before the flash emitted at C’
1
. Yet both
observers measure the same speed of light, c.
10
4. Lorentz Transformation
Now we wish to derive the transformation equations for the displacement and velocity of an
object—the relativistic version of the Galilean transformation equations. In what follows, we’ll
be setting
2
2
1
1
c
v
−
· γ
.
a. Two frames
Consider two inertial reference frames, S & S’ and assume that O = O’ at t’ = 0.
What is the xdistance from O to the point P, as measured in the S’ frame? In effect, then, we’ll
have t t · ∆ and t t ′ · ′ ∆ .
t v x ′ + ′ · ′
In the S frame, x · , so
γ
x
· ′
also. Set ‘em equal.
t v x
x
′ + ′ ·
γ
( ) t v x x ′ + ′ ·γ
On the other hand, as measured in the S frame,
γ
x
vt x
′
+ ·
. Set them equal.
( )
γ
γ
x
vt t v x
′
+ · ′ + ′
Solve for t.
( )
γ
γ
x
t v x vt
′
− ′ + ′ ·
,
`
.

′ + ′ · x
c
v
t t
2
γ
b. Transformation equations
We have, then, for relative motion along the xaxis:
( ) t v x x ′ + ′ ·γ ;
y y ′ ·
; z z ′ · ;
,
`
.

′ + ′ · x
c
v
t t
2
γ
Notes: i) the inverse transformation is obtained by replacing v with –v.
ii) for v << c, these reduce to the Galilean transformation.
11
c. 4vectors
Suppose that when O = O’, a flash of light is emitted from the origin O. In the S frame, the
distance the light wave front travels in time t is
2 2 2 2 2 2
t c z y x r · + + · . Measured in the S’
frame, it’s
2 2 2 2 2 2
t c z y x r
′
·
′
+
′
+
′
·
′
. Subtract the second expression from the first and collect the S frame
on one side of the equal sign, the S’ frame on the other side.
2 2 2 2 2 2
t c t c r r
′
− ·
′
−
2 2 2 2 2 2
t c r t c r
′
−
′
· −
There is this quantity, a generalized displacement (call it s) which is the same in the two inertial
reference frames.
2 2
s s
′
·
We see that the quantity (ict) “acts like” a component of displacement along a fourth axis. The
interval between any two events in spacetime is
2 2 2 2 2 2
t c z y x s ∆ − ∆ + ∆ + ∆ · ∆ . The interval is
invariant under the Lorentz Transformation. That is, as measured in any two inertial frames,
2 2
s s
′
∆ · ∆
. This is an extension of the invariance of lengths under a rotation of the coordinate
axes.
d. Transformation of velocities
Since displacements and time intervals are transformed, obviously relative velocities won’t add
simply, either.
In the S’ frame an object moves with constant velocity along the x axis;
t d
x d
u
x
′
′
· ′
. Transform to
the S frame;
( )
x
x
x
u
c
v
v u
dt
dx
c
v
v
dt
dx
dx
c
v
dt
vdt dx
u
2 2 2
1 1 −
−
·
−
−
·
,
`
.

−
−
· ′
γ
γ
and similarly for the y and z components.
While dy & dz are not contracted, dt is still dilated.
12
example:
c u
A
5 . 0 − · and c u
B
8 . 0 − · , both as measured in the S frame. The S’ frame rides along with
spaceship B. Therefore,
B
u v
· .
2
5 . 0
8 . 0
1
) 8 . 0 ( 5 . 0
1
2 2
c
c
c
c
c c
u
c
v
v u
u
A
A
A
·
−
− − −
·
−
−
· ′
Be careful with the directions of the velocities.
Note that when
c u < <
and
c v < <
, then
0
2
→
c
vu
and v u u − · ′ . On the other hand, if
c u ·
,
then c
c
v
c
v
c
c
cv
v c
u ·
−
,
`
.

−
·
−
−
· ′
1
1
1
2
.
13
D. Energy and Momentum
We require that all the “Laws” of Physics be the same in all inertial reference frames. We
require further that when v << c, we recover the familiar Newtonian forms of the “Laws.” This
latter requirement is called a Correspondence Principle. What are those “Laws”?
1. Conservation of Momentum
We define a relativistic momentum so that the two conditions above are satisfied.
u m p
γ ·
This m is the rest mass—the mass measured by an observer at rest with respect to the object.
This quantity should be the same in all inertial reference frames. With this definition,
final initial
p p
·
in all inertial reference frames.
2. Relativistic Energy
a. Workenergy theorem (one dimensional)
The work done by a force on an object changes its kinetic energy, thus
∫
· · ∆
2
1
12
x
x
Fdx W K
.
∫
· ∆
2
1
x
x
dx
dt
dp
K
∫
· ∆
2
1
t
t
dt
dt
dx
dt
dp
K
∫
· ∆ udp K
Integrate by parts.
∫
− · ∆
2
1
2
1
u
u
u
u
pdu up K
∫
−
− · ∆
2
1
2
1
2
2
1
u
u
u
u
du
c
u
mu
up K
Recall that
2
2
du
udu · .
∫
−
− · ∆
2
2
2
1
2
2
1
c
u
du m
up K
u
u
Look up the form
∫
+bx a
dx
in a math tables book.
14
2
1
2
1
2
2
2
1
1 2
2
u
u
u
u
c
c
u
m
up K
]
]
]
]
]
]
]
−
−
− · ∆
2
1
2
2
2
2
2
2
1
1
u
u
c
u
mc
c
u
mu
K
]
]
]
]
]
]
]
− +
−
· ∆
]
]
]
]
]
]
]
−
∆ ·
]
]
]
]
]
]
]
−
− +
· ∆
2
2
2
2
2
2 2 2
1 1
2
1
c
u
mc
c
u
mu mc mu
K
u
u
Now, if we started from rest, then u
1
= 0 and u
2
= u and
2
2
2
2
1
mc
c
u
mc
K −
−
· ∆
. Therefore, we
define the relativistic kinetic energy to be
2
2
2
2
1
mc
c
u
mc
K −
−
·
.
The quantity mc
2
is called the rest energy, because it’s independent of u. The total relativistic
energy is E = K + mc
2
+ V, where V is the potential energy, if any. If V = 0, then
2 2
mc mc K E γ · + · .
b. Energymomentum relation
Take a look at the quantity (V = 0)
,
`
.

−
·
−
· −
−
· −
2
2
2 2
2
2
2
2 2 2
4 2
2
2
4 2
4 2 2
1 1 1
c
u
u m
c
c
u
u c m
c m
c
u
c m
c m E
.
2 2 4 2 2
p c c m E · −
4 2 2 2 2
c m p c E + ·
For photons, m = 0 and E = pc.
15
c. Units of massenergy
It is convenient to express energy in units of electronvolts (eV). An electronvolt is the energy
gained by an electron upon being accelerated through a one Volt potential difference. Thus 1 eV
= 1.60x10
19
Joules. The rest energy of an electron is
( ) MeV eV x J x m x kg x mc 511 . 0 10 511 . 0 10 20 . 8 sec / 10 3 10 11 . 9
6 14
2
8 31 2
· · · ·
− −
.
Often, mass is expressed in terms of MeV/c
2
so that the electron mass is 0.511MeV/c
2
.
Sometimes, the c
2
is dropped, but it’s understood to still be there. Similarly, momentum is
expressed in terms of MeV/c, since pc = units of MeV.
3. Relativistic Mechanics
a. Force
We want the “Laws” of Mechanics to be invariant under the Lorentz Transformation. Also, we
want to recover the classical result when u << c. So, we define the relativistic force component
to be
dt
dp
F
x
x
· , where
2
2
1
c
u
mu
p
x
x
−
·
.
Let’s say the motion and force are entirely along the xdirection.
]
]
]
]
]
]
]
−
+
−
·
]
]
]
]
]
]
]
−
·
2
2
2
2
2
2
1
1
1 1
c
u
dt
d
mu
dt
du
c
u
m
c
u
mu
dt
d
F
dt
du
c
u
c
u
mu
dt
du
c
u
m
F
,
`
.

−
,
`
.

−
,
`
.

− +
−
·
−
2
2
3
2
2
2
2
2
1
2
1
1
]
]
]
]
,
`
.

− +
,
`
.

− ·
− −
2
3
2
2
2
2 2
1
2
2
1 1
c
u
c
u
c
u
dt
du
m F
dt
du
c
u
m F
2
3
2
2
1
1
,
`
.

−
·
Solve for the acceleration.
2
3
2
2
1
,
`
.

− ·
c
u
m
F
dt
du
The result is, that as
c u →
,
0 →
dt
du
, no matter how large the applied force. At the other
extreme, when u << c,
m
F
dt
du
·
.
b. Collisions—conservation of momentum
Consider the collision of two billiard balls. They have equal masses, m. Let’s say that one ball
is initially at rest while the second ball has momentum p
o
and energy E
o
before the collision.
16
After the collision, both balls have the same energy, E, and mass, m. It’s an elastic collision.
Momentum and energy are conserved.
In the x direction,
θ cos 2p p
o
·
. Substitute for p
o
and p using E
2
= p
2
c
2
+ m
2
c
4
.
θ cos
2 1
4 2 2 4 2 2
c m E
c
c m E
c
o
− · −
Conservation of energy allows us to eliminate E, since it was given that E mc E
o
2
2
· + . Keep
in mind that E
o
is the relativistic total energy of the second ball, while mc
2
is the rest energy of
the first (target) ball. At the same time, we solve for θ cos , the cosine of the scattering angle.
( )
( )( )
( )( )
2 2
2 2
4 2
2
2
4 2 2
3
4
cos
mc E mc E
mc E mc E
c m mc E
c m E
o o
o o
o
o
− +
− +
·
− +
−
· θ
2
2
3
cos
mc E
mc E
o
o
+
+
· θ
In the classical limit,
2
mc E
o
≈ and therefore
o
mc
mc
45
2
1
4
2
cos
2
2
· ⇒ · ≈ θ θ . But, as E
o
>> mc
2
,
o
0 1 cos → ⇒ → θ θ !
c. Decay of a highenergy particle
An unidentified highenergy particle is observed to
decay into two pions (
π
mesons), as shown. Knowing the momenta and masses of the decay
products, we determine the mass of the incident particle, hoping to identify it.
c
MeV
p 910
1
·
,
c
MeV
p 323
2
·
, Mev mc c m c m 6 . 139
2 2
2
2
1
· · · .
The energy and momenta are conserved. The total energy is
4 2 2 2
2
4 2 2 2
1 2 1
c m c p c m c p E E E
o
+ + + · + ·
MeV MeV MeV E
o
1273 352 921 · + ·
The quickest way to obtain the magnitude of the incident momentum is to use the law of cosines:
17
2 2
2 1
2 2
2
2 2
1
2 2
1034229 cos 2 MeV c p p c p c p c p
o
· − + · θ
MeV c p
o
1017 ·
Now that we have the total energy and the kinetic energy, the mass is obtained from
4 2 2 2 2
c m c p E
o o o
+ ·
MeV c p E c m
o o o
765
2 2 2 2
· − ·
Evidently, the incident particle was a
ρ
meson. What was its speed before it decayed? Well,
the total energy is also
2
2
4 2
2
1
c
u
c m
E
o
o
−
·
, so solve that for u.
8 . 0 1
2
4 2
· − ·
o
o
E
c m
c
u
d. Massenergy equivalence
When we speak of the total energy being conserved that includes the total rest energy. For
instance, consider the decay of a neutron that is initially at rest.
ν + + → e p n
The neutron decays into a proton, an electron and an antineutrino. The three product particles
are observed to have total kinetic energy of K = 0.781 MeV. The initial energy is just the rest
energy of the neutron, E
i
= 939.57 MeV. The total final energy is
MeV MeV MeV MeV K c m c m E
e p f
57 . 939 781 . 0 511 . 0 28 . 938
2 2
· + + · + + ·
Notes: i) The rest energy of the antineutrino is too small to bother with.
ii) Keep in mind the rounding of numbers and significant digits when substituting
numerical values into the formulae.
iii) Notice that e p n
m m m + ≠
. A portion of the neutron’s rest energy has been
converted into kinetic energy.
18
E. A Hint of General Relativity
1. Equivalence
In Special Relativity it is asserted that all inertial reference frames are equivalent—the “laws” of
physics are the same in all inertial reference frames. No experiment done in one frame can
detect its uniform motion relative to another frame. Can the same be said for reference frames
that have a relative acceleration?
a. Elevator
Recall the past discussion of a person standing in an
elevator. If the elevator moves perfectly smoothly and
there are no floor indicator lights, then the person inside
will have no perception of the elevator’s motion, except
for feeling perhaps the elevator floor pressing upward
on his or her feet. [Keep in mind: the person gets no
information from any source outside the reference frame
of the elevator.] Contrast this situation with that of
another person standing in a similar elevator, but this
elevator is simply resting level on the Earth’s surface.
The person in this elevator also feels the floor pressing
upward on his or her feet, also has no perception of the
elevator’s motion. We, as omniscient external observers, know that this second elevator is
resting on the surface of a planet, and that what the person inside is experiencing is the
gravitational force exerted by that planet. The point is that there is no experiment that either of
the persons inside the elevators could perform that would distinguish between the two situations.
Pendula would swing back and forth just the same; projectiles would follow the same kinds of
arcs, etc.
b. Light and gravity
Imagine ourselves as observers far from any source of gravitational force. Nearby, we observe a
closed “elevator” which is accelerating, relative to us, at a constant rate, o
a
. A person standing
inside the “elevator” sends a series of light pulses toward one wall—he or she and we see the
light pulses dropping toward the floor as they approach
the wall. The light follows a curved path inside the
elevator.
The Postulate of General Relativity asserts that the
“laws” of physics have the same form for observers in
any frame of reference, regardless of its acceleration
relative to another frame. We have seen that an
accelerated frame is equivalent to one in a gravitational
field. It follows that the force of gravity must affect a
beam of light just as it affects the motion of a massive
projectile. Indeed, experiment has shown that it does.
But, light has no mass.
19
2. Curvature
Classically, we would say that a mass, such as a planet, exerts a gravitational force on another
mass, such as a moon or a person. However, a person in an “elevator” cannot determine whether
his or her “elevator” is in the gravitational field of a planet or is being accelerated at a constant
rate by, say rocket motors. If the “elevator” is in a gravitational field, we can nonetheless
mathematically transform the “laws” of physics into versions of the same mathematical form that
do not include gravity yet which make equally accurate predictions of the motions of particles
and of light beams.
What Einstein did was to formulate such a version of the “laws” of motion. Objects and light
beams move always in straight lines, but in a curved spacetime. Empty spacetime is flat, but
the presence of mass at any location curves spacetime to a degree proportional to the amount of
mass that is present.
Predictions of General Relativity:
Precession of orbits—Mercury
Gravitational redshift—time runs slower in intense gravitational field
Gravitational lensing—light paths curved
Gravitational waves—ripples in space time(?); slowing binary neutron stars
20
II. Quantum Theory
A. Black Body Radiation
1. Equilibrium Between Matter and Radiation
a. Thermal equilibrium
Imagine a closed oven, maintained at a constant temperature, T
o
. Inside, EM waves bounce
from wall to wall, being absorbed and reemitted over and over. Ultimately, the radiation is
rendered homogeneous, isotropic and unpolarized. A thermometer placed in the center of the
oven will stabilize at a temperature o
T T ·
. The radiation is said to be in thermal equilibrium
with the walls of the oven.
b. Emissivity
From thermodynamics (Kirchhoff) the power radiated by a body in thermal equilibrium with
radiation is expressed
f
f
A
E
T f J · ) , (
,
where J is the power radiated per unit area per unit frequency, E
f
is the emissivity or intensity per
unit frequency of the radiation emitted by the body and , A
f
is the fractional absorption of the
body for radiation of frequency f. Notice that the substance of which the body is made is not
important. For a black body,
0 . 1 ·
f
A
for all f. The observed spectrum of radiation emitted by
a black body looks qualitatively like this:
c. Model for a black body
One physical model for an ideal black body is a small opening in the
wall of a heated cavity. Because the opening is small, a light ray
entering through the opening is very unlikely to bounce back out
again. Conversely, any light ray that exits through the opening will
have reached equilibrium with the interior walls, having bounced off
the walls many times. The black body is not the oven as a whole,
but the opening in the oven wall.
21
2. StefanBoltzmann “Law”
a. Emissivity
The total emissivity is obtained by integrating E
f
df.
∫
∞
·
0
df E E
f
This quantity was found experimentally by J. Stefan to be proportional to T
4
.
4
T E σ ·
Subsequently, Boltzmann derived this result from Maxwell’s equations. The proportionality
constant is called the StefanBoltzmann constant,
4 2
8
10 67 . 5
K m
W
x
−
· σ
or Wm
2
K
4
. For non
black bodies,
4
T a E σ · , where a < 1.
b. Wien’s displacement “law”
Experimentally, K m x T ⋅ · ⋅
−3
max
10 898 . 2 λ , or
K m x T
f
c
⋅ · ⋅
−3
max
10 898 . 2
.
3. RayleighJeans “Law”
a. Wien’s exponential “law”
) , (
4
) , ( T f J
c
T f u ·
,
where u is the energy per unit volume per unit frequency. As derived from thermodynamics and
Maxwell’s equations,
T
f
e Af T f u
⋅
−
·
β
3
) , (
where A and
β
are constants. When tested by experiment, this expression fails at long
wavelengths. But, Wien’s exponential “law” fits well near the peak, at max
f
.
b. Rayleigh’s approach
Rayliegh proposed that the energy density be expressed as the product of the number of standing
wave modes in the cavity and the average energy of each mode. Let N(f)df be the number of
modes between f and f+df.
df E f N udf ) ( ·
We need to obtain expressions for N(f) and for E . Picture standing waves in a cavity. In one
dimension:
22
We imagine the whole volume of the cavity occupied with
standing EM waves, of many different frequencies. The radiation
is in equilibrium with the walls of the cavity, at temperature T.
Classically, the probability that there will be a mode of energy, E,
in the cavity is given by the Boltzmann distribution.
T k
E
B
e E P
−
· ) (
The average energy per mode is therefore
( )
T k
T k
T k
dE e
dE Ee
E
B
B
B
T k
E
T k
E
B
B
· · ·
∫
∫
∞
−
∞
−
2
0
0
As for N(f), the density of states, consider a cubical box of side L.
Inside the box, the xcomponent of the Efield satisfies the wave equation 0
2 2
· + ∇
x x
E k E . If
we assume that
) ( ) ( ) ( z w y v x u E
x
·
, then we get three separated equations. The one for u(x) is
0
2
2
2
· + u k
dx
u d
x
,
which has the solution
x k u x u
x o
sin ) ( ·
. Similarly,
y k v y v
y o
sin ) ( ·
and
z k w z w
z o
sin ) ( ·
.
The quantity k
2
is like the square of a radius in kspace:
2 2 2 2
z y x
k k k k + + ·
. Since we must have
standing waves in the box, with the electric field vanishing at the walls,
L
n
k
x
x
π
· ,
L
n
k
y
y
π
·
and
L
n
k
z
z
π
· , where the n
x
, n
y
and n
z
are positive integers. In other words, only discrete points
in kspace designate the allowed energy modes in the cubical cavity. So, we count the number of
kpoints lying in a spherical shell of radius k and thickness dk.
23
We see that each point occupies a volume
3
,
`
.

L
π
so the number of points in the shell is
2
2
3
2
2
4
8
1
) (
π
π
π
dk Vk
L
dk k
dk k N ·
,
`
.

·
,
where V = L
3
. Finally, there are two perpendicular polarizations for each mode, so the number of
modes per unit volume (the density of states) is
2
2
) (
π
dk k
dk
V
k N
· .
In terms of frequency,
3
2
8 ) (
c
df f
df
V
f N π
· , since
π 2
kc
f ·
.
At last the energy density is
Tdf k
c
f
df E f N df T f u
B
3
2
8
) ( ) , (
π
· · .
Alternatively, the energy density in terms of wavelength is
λ
λ
π
λ λ Td k d T u
B
4
8
) , ( ·
Compared with the observed black body spectrum, the
RayleighJeans “law” is seen to diverge as 0 → λ .
What do we have so far? We have regarded the range of
allowed energies for a standing wave in the cavity to be a
continuous variable. The result obtained is proportional to
one over the fourth power of the wavelength. This diverges
for small wavelengths (the ultraviolet catastrophe).
4. Planck’s “Law”
24
a. Quantized energy modes
Rather than visualize standing EM waves inside a cavity, consider the atoms that form the walls
of the cavity. These atoms vibrate and absorb or emit EM waves. Let’s assume that the
energies of these oscillators can change only in discrete steps, rather than continuously.
Postulate: E
n
= nhf where n is a positive integer. No other energy values are allowed.
The average energy per vibration mode is a discrete sum
∑
∑
∞
·
−
∞
·
−
·
0
0
n
T k
E
n
T k
E
n
B
n
B
n
e
e E
E .
Firstly, the denominator. . .
T k
hf
n
T k
nhf
B
B
e
e
−
∞
·
−
−
·
∑
1
1
0
. This follows from the series of the form
r
r
n
n
−
·
∑
∞
·
1
1
0
with T k
hf
B
e r
−
·
.
Secondly, substituting this into E . . .
∑ ∑
∞
·
− −
∞
·
− −
,
`
.

− ·
,
`
.

− ·
0 0
1 1
n
T k
nhf
T k
hf
n
T k
nhf
T k
hf
B B B B
ne e hf nhfe e E
.
Notice that
T k
hf
B
n
T k
hf
n
n
T k
hf
n
B
B
B B
e
T k
hf
d
d
ne e
T k
hf
d
d
−
− −
−
,
`
.

· − ·
,
`
.

∑ ∑
1
1
. Therefore, we have
2
1
1
1
1
1
,
`
.

−
−
,
`
.

− − ·
,
`
.

−
,
`
.

,
`
.

− − ·
−
−
−
−
−
T k
hf
T k
hf
T k
hf
T k
hf
B
T k
hf
B
B
B
B
B
e
e
e hf
e
t k
hf
d
d
e hf E
1 1 −
·
,
`
.

−
·
−
−
T k
hf
T k
hf
T k
hf
B B
B
e
hf
e
hfe
E
This result is multiplied by the number of modes having frequency f,
3
2
8
) (
c
f
f N
π
· , to
obtain. . .
25
b. Planck’s distribution formula
,
`
.

−
·
−
⋅ ·
1
8
1
8
) , (
3
3
3
2
T k
hf
T k
hf
B B
e c
hf
e
hf
c
f
T f u
π π
.
What do we have?
i) Assume that oscillators or standing waves are limited to discrete values of energy,
E
n
= nfh.
ii) For high f, the
0
1
1
→
−
T k
hf
B
e
, therefore the probability that a high frequency or short
wavelength mode is occupied or present is very low.
iii) An oscillator that emits energy can change its energy only in steps of
nhf E · ∆
,
where f is the vibration frequency of the oscillator.
Fitting Planck’s formula to the observed black body radiation yields a value for Planck’s
constant, h = 6.626x10
34
J sec.
26
B. Photons
1. Photoelectric Effect
a. Kinetic energy
When a metal surface is exposed to intense monochromatic EM radiation, electrons are expelled
from the metal. A certain amount of energy, called the work function, is required to liberate an
electron from the metal. Once liberated, the photoelectrons have a distribution of kinetic
energies. We can evaluate the maximum, K
max
, of the kinetic energy distribution by applying a
voltage, V
s
, large enough to stop the fastestmoving electron from escaping. K
max
= eV
s
.
Finding: K
max
is independent of the incident intensity, while the photocurrent is proportional to
the incident intensity.
Interpretation: Increasing the intensity of the incident radiation does not increase the left over
kinetic energy of the photoelectrons, only the number of electrons ejected from the metal.
b. Work function
Finding: K
max
is proportional to the frequency, f, of the incident radiation with an f
o
below which
no photoelectrons are produced (K
max
= 0).
27
Interpretation:
φ − · · hf eV K
s max , where
φ
is the work function of the metal, f is the
frequency of the incident radiation and h is Planck’s constant. That is, the light is absorbed in
discrete portions,
hf E · ∆
, only. If
φ < hf
, then no photoelectrons are produced; if
φ > hf
,
increasing the intensity only liberates more electrons, each one absorbing one hf and no more. If
the incident frequency is such that
φ ≤ hf
, then K
max
= 0 and no electrons escape from the metal.
We conclude that EM radiation is not a continuous wave form, but consists of discrete, localized
wave packets, called a photon. Either a photon is absorbed entirely, or not at all. Likewise, light
is emitted in the form of one or more discrete photons.
2. Compton Effect
a. Absorption of a classical EM wave
Suppose a continuous EM wave (frequency f
o
) is incident on a free electron. The classical
prediction is that the electron will experience acceleration causing the electron to oscillate
transversely and to move in the direction the light wave is traveling. The accelerated electron in
its turn emits a new EM wave. Since the electron is now moving, the emitted wave has a
Dopplershifted frequency. The longer the electron is exposed to the incident radiation, the
faster it translates and the greater is the Doppler shift. The intensity of the incident radiation also
influences the Doppler shift, since it influences the electron’s acceleration.
This is not what is observed.
b. Collision between a photon and an electron
Consider a collision between an xray photon and a stationary free electron.
28
Qualitatively, what is observed is that the frequency,
f ′
, of the scattered photon depends only
on the scattering angle, θ. Usually, the effect is expressed in terms of the shift in wavelength,
thusly:
( ) θ λ λ cos 1− · − ′
c m
h
e
.
The quantity
0243 . 0 ·
c m
h
e
Å is called the Compton wavelength of the electron.
c. Theoretical treatment as a collision
As a collision between two particles, both energy and momentum are conserved. It is necessary
to use the relativistic forms of energy and momentum, since the photon is certainly moving at a
speed close to, if not equal to c.
Energy
e e
E E c m E + ′ · +
2
e e
E f h c m hf + ′ · +
2
momentum components
φ θ cos cos
e
p p p + ′ ·
θ φ sin sin 0 p p
e
′ − ·
The first step is to eliminate
φ
from the momentum component equations.
2
sin 1 cos
,
`
.
 ′
− + ′ · θ θ
e
e
p
p
p p p
Square both sides and solve for
θ c o s 2
2 2 2
p p p p p
e
′
− +
′
·
. For the photon,
λ
h
c
hf
c
E
p · · ·
.
On the other hand, the energy of the electron is also
4 2 2 2 2
c m c p E
e e e
+ · . Substitute for E
e
and p
e
.
( )
4 2
2
2
2 2
2
2
4 2
cos 2 c m
c
f f h
c
hf
c
f h
c c m f h hf
e e
+
]
]
]
]
′
−
,
`
.

+
,
`
.

′
· + ′ − θ
θ cos 2 2 2 2
2 2 2 2
f f h c m f h c hfm f f h
e e
′ − · ′ − + ′
29
( ) ( ) θ cos 1 2 2
2 2
− ′ · ′ − − f f h f f c hm
e
( ) θ cos 1
1 1
2
− · −
′
·
′
′ −
c m
h
f f f f
f f
e
( ) θ λ λ cos 1− · − ′
c m
h
e
This Compton shift formula exactly matches the observations. We conclude, then, that a photon
behaves like a particle having relativistic energy hf and momentum
λ
h
.
30
C. Matter Waves
We find that light is quantized and may be regarded in some circumstances as being particles of
zero mass, momentum h/λ , and energy hf. Some persons use the quantum point of view
exclusively. Might it be useful to investigate whether nonzero mass particles can be treated as
having wave properties?
1. deBroglie’s Postulate
a. deBroglie wavelength
For a photon, p = h/λ . In a similar vein, define for any particle a wavelength λ = h/p, where p
is the momentum (magnitude) of the particle. Further, if E is the total relativistic energy of the
particle, a frequency is defined as f = E/h.
b. Phase velocity of a wave
The phase velocity of a wave is v
p
= fλ = E/p. If the relativistic expressions for E & p are used,
then we get a phase velocity for a massive particle
v
c
mv
c
v
c
v
mc
v
p
2
2
2
2
2
2
1
1
·
−
−
· .
2. Group velocity
A particle occupies a limited volume, so if we are to represent it with a waveform, the waveform
amplitude must be nonzero only in a limited region of space. We accomplish this by
superimposing many waves of differing wavelengths and amplitudes and phases.
a. Waves in one dimension
,
`
.

− · ft
x
A y π
λ
π
2
2
cos
and
f v
p
λ ·
.
We define the angular frequency, ω = 2π f and the wave number, k = 2π /λ . Using these
quantities,
( ) t kx A y ω − · cos
and
k
v
p
ω
·
.
b. Beats
Superimpose two waves: ( ) ( ) t x k A t x k A y y y
2 2 1 1 2 1
cos cos ω ω − + − · + · .
( ) ( ) { ¦
,
`
.
 +
−
+
⋅
,
`
.

− − − · t x
k k
t x k k A y
2 2
cos
2
1
cos 2
2 1 2 1
1 2 1 2
ω ω
ω ω
.
[Note: cos(a) + cos(b) = 2cos(½ (ab)∙cos(½ (a+b).]
31
We have a traveling wave whose amplitude is not constant. ( ) t x k A y ω′ − ′ ′ · cos , where
2
2 1
k k
k
+
· ′
and
2
2 1
ω ω
ω
+
· ′
. The timevarying amplitude is
( ) t kx A A ω ∆ − ∆ · ′ cos 2
. This
A′ is also known as the envelope.
The envelope also travels at a speed called the group velocity,
k
k
v
g
∆
∆
·
∆
∆
·
ω
ω
2
2
.
Evidently, from the form of A′ , π 2 · ∆ ⋅ ∆ x k and π ω 2 · ∆ ⋅ ∆ t . With sound waves, the regular
rises and falls of the amplitude are known as beats.
c. Wave packets
The beating waveform still extends to ±
∞
in x. That combination is constructed only of two
waves having the same amplitude but slightly different frequencies or wave numbers. We can
construct a wave packet that is nonzero only in a small region by superimposing many waves
having different amplitudes, and having a range of wave numbers centered on a k
o
. The
mathematics of the superposition will be explored in paragraph 4. For the time being, we are
concerned with the group velocity of the wave packet:
o
o
o k
p
k
p
k
g
dk
dv
k v
dk
d
v + · ·
ω
, since p
kv · ω
.
d. Dispersion
If v
p
= v
p
(λ ), then the medium through which the waves are propagating is said to be dispersive.
The individual harmonic waves travel at different speeds, so the wave packet or wave group
spreads out with time.
e. Application to a massive particle
We consider a massive particle (in this context, massive means having a nonzero mass), such as
the electron. Its mass is m and it is moving uniformly with speed v. We postulate that the
motion of the particle can be modeled by a traveling wave packet with frequency f
o
= E/h and
wavelength λ
o
= h/p where E is the total relativistic energy and p the total relativistic
momentum of the particle. The wave packet would be constructed by a superposition of
harmonic waves having wavelengths centered on λ
0
.
The phase velocity is v
p
= fλ = E/p. Putting E in terms of p and p in terms of the wave number
k yields [
k 2
h
p and
m
p
E
π
· ·
2
2
]
32
2
1
,
`
.

+ ·
k
mc
c v
p
, where
π 2
h
· .
From this expression, we obtain the group velocity
o
o
o k
p
k
p
k
g
dk
dv
k v
dk
d
v + · ·
ω
( )
2
3
2
2
1
1
2
2
1
,
`
.

+
,
`
.

−
+
,
`
.

+ ·
o
o
o
o
g
k
mc
k
mc
c
k
k
mc
c v
o
k
p
o
g
v
c
k
mc
c
v
2
2
1
·
,
`
.

+
·
.
Previously, we saw that the phase velocity also equals c
2
/v. Therefore, the group velocity of the
wave packet coincides with the velocity of the massive particle: v
g
= v.
3. DavissonGermer experiment
How might wavelike behavior of massive particles be observed? One of the prominent
characteristics of waves is the fact that they interfere with each other to form interference
patterns. When a monochromatic light beam is incident on a diffraction grating, a characteristic
interference pattern is observed, entirely understood in terms of the constructive and destructive
interference among the scattered light waves.
a. Electron diffraction
Consider a monoenergetic beam of electrons incident on a crystal lattice. The electrons will be
scattered from regularly spaced centers. We count the number of electrons that are scattered at
an angle ϕ from the incident direction.
33
We do not observe either a uniform distribution with scattering angle, nor a sharp peak at ϕ = 0
and no particles elsewhere. Rather, we observe a distribution of scattered electrons something
like this:
b. Interpretation
If this result is interpreted as wavelike interference, then the peak at ϕ = ϕ
max
occurs when
λ ϕ· ⋅sin d
, where d is the spacing between neighboring atoms in the crystal. [We are
imagining that the rows of atoms forming the surface of the crystal correspond to the closely
spaced lines of a grating.] We might solve for the wavelength: λ = d∙sin(ϕ
max
).
Specifically, for 54 eV electrons impinging on a Ni crystal, ϕ
max
= 50
o
and d = 2.15Å whence we
obtain λ = 1.65Å. The question is, does this wavelength correspond to the deBroglie
wavelength of such an electron?
Firstly, it will be easier if the relativistic formulae are unnecessary. So check how fast the
electrons are moving. The kinetic energy is K = γ mc
2
– mc
2
. We have K = 54 eV and mc
2
= .
511 MeV. Thus γ – 1 = 0.0001. We can use the classical expression K = p
2
/2m. Therefore,
mK p 2 · . The deBroglie wavelength is
eV
c
MeV
s eV x
p
h
54 511 . 0 2
10 136 . 4
2
15
⋅ ⋅
⋅
· ·
−
λ
= 1.67Å. That is
close enough in view of the rounding used in the calculation. It appears that the deBroglie
postulate has some physical reality.
4. Uncertainty and probability
Consider a simplified electron diffraction experiment: a monoenergetic beam of electrons
impinging on two narrow slits. The electrons all have the same kinetic energy and the same
velocity. Beyond the slits is a detector, which can be moved along the xaxis.
34
The observed result:
Note that at a specific location, x, the detector counts electrons one at a time. After counting for
a “long” time at several xvalues, the interference pattern is obtained.
a. Probability
We have a stream of many electrons incident on the double slits, passing through them, and
being counted by the detector. The detector counts the number of electrons arriving at x per unit
time, so the intensity being measured is I(x) in particles per minute. The number of particles we
expect to count in the interval x’ to x’+∆ x is proportional to the probability that an electron will
be counted at x lying between x’ and x’+∆ x. Define a wave function, such that
2
Ψ equals that
probability. This parallels the definition of intensity for light waves.
For a single slit we would obtain, with either one slit or the other open,
For two slits spaced a distance D apart, open however just one at a time in succession, we would
observe a superposition of the singleslit distributions. If both the slits are open while electrons
are being counted, we obtain, not the superposition of two singleslit distributions, but the
following interference pattern:
35
Evidently,
2 2 2 2
1 2 1 2
Ψ · Ψ + Ψ ≠ Ψ + Ψ , rather,
( )
2 2 2
* * * * * *
1 1 1 2 1 2 2 2 1 2 1 2 1 2
Ψ · Ψ Ψ + Ψ Ψ + Ψ Ψ + Ψ Ψ · Ψ + Ψ + Ψ Ψ + Ψ Ψ .
Those additional terms in the parentheses are called interference terms. Ψ
*
is the complex
conjugate of
Ψ so that
Ψ Ψ · Ψ
*
2
.
b. Uncertainty.
The wave function is interpreted as being related to the probability that a measurement will find
a particle at a specified location, x’. It is constructed by a superposition of plane waves
∫
∞
− ⋅ · Ψ
0
) cos( dk t kx a
k
ω
, where k is the wave number and a
k
is a Fourier coefficient. As is
often the case, we find it convenient to use the complex version:
( )
∫
∞
−
⋅ · Ψ
0
dk e a
t kx i
k
ω
.
This wave packet is to be zero everywhere except within a region of width ∆ x. To illustrate,
consider a simple rectangular wave packet.
The wave function is nonzero for a region on the xaxis of width ∆ x centered on x = 0. The
total probability that the particle will be observed somewhere on the xaxis must be 1.0, so the
wave function is
x
x
∆
· Ψ
1
) (
.
The Fourier transform of Ψ will yield a momentum wave packet, a(k). That is, ( )
2
a k will tell
us the probability that a particle will be observed to have momentum p = hk.
36
k
xk
x
dx
x
e
k a
x
x
ikx
,
`
.
 ∆
∆
·
∆
·
∫
∆
∆
−
2
sin
2
2
1
) (
2
2
π
π
.
In terms of the momentum, p = k,
2
2
sin
2
2
sin
2
) (
x p
x p
x
p
x p
x
p a
∆
,
`
.
 ∆
∆
·
,
`
.
 ∆
∆
·
π π
.
The height of the central peak is much greater than the sidepeaks, and the width of the central
peak is roughly
x
p
∆
≈ ∆
. Now, look at the product
·
∆
∆ ≈ ∆ ⋅ ∆
x
x p x
. This is an
uncertainty relation, saying that it is impossible to measure simultaneously both the position (x)
and momentum (p) of a particle to arbitrary precision.
In fact, a rectangular wave packet is not physical, since it is a discontinuous function. Much
theoretical work has gone into determining what sort of mathematical construction will give
smooth wave packets with minimum initial uncertainty, ∆ x. For a physically realistic wave
packet, it was found that
2
≥ ∆ ∆ p x .
This relation holds for any pair of conjugate variables, e.g.,
2
≥ ∆ ∆ E t .
[
E t
v
E
t v p x ∆ ∆ ·
∆
∆ · ∆ ∆
] [The time rate of change of a particle’s kinetic energy:
p v E ∆ · ∆
.]
37
D. Atoms
The history of the concept of material objects being composed of small particles goes back to the
ancient Greeks, and is beyond the scope of this course. The “modern” picture of an atom was
assembled in a series of experiments during the 19
th
and early 20
th
centuries.
1. Charges/particles; e/m
a. Faraday’s “Law” of Electrolysis
When an electrical current is passed through molten NaCl, chlorine and sodium are deposited on
the anode and cathode, respectively. Quantitatively,
ν ⋅
⋅ ·
Coul
q
M m
96500
,
where m = mass deposited on the anode or cathode, M = molecular weight, ν = valance of the
atoms [1 for Na & Cl, 2 for O, etc.], and q = total charge passed through the NaCl.
Faraday’s “Law” of Electrolysis demonstrates that i) molecules [NaCl] consist of elemental
atoms and ii) subatomic particles have electric charge.
b. Cathode Rays
J. J. Thomson showed that cathode rays are streams of electrons. As we know now, when a high
voltage is applied to the ends of a partially evacuated glass tube, a glowing path of ionized air is
formed inside the tube between the electrodes. The ionization is caused by collisions between air
molecules and fastmoving electrons. Those electrons escape from one electrode and are
accelerated toward the opposite electrode by the applied voltage. The ionized air molecules emit
the light seen along the glowing path. At the time, the glowing path was mysterious. Thomson’s
experiments established that cathode rays were caused by charged particles, subatomic in mass
and apparently present in all matter.
38
Pass a stream of electrons through a electric field and a magnetic field oriented at right angles to
each other, as shown here:
With no Bfield, the electron stream hits the screen at the point D. The deflection angle is
x
y
v
v
· θ tan
, where
t
m
eE
t a v
y y
⋅ · ⋅ ·
. But
x
v
L
t ·
, so
x x
y
mdv
eVL
mv
eEL
v · ·
. Therefore,
2 2
tan
x x
dv
VL
m
e
mdv
eVL
,
`
.

· · θ
.
So, knowing v
x
and measuring θ , we could obtain e/m, the charge to mass ratio of the electron.
To know v
x
, we turn up the Bfield until there is no deflection—the magnetic force on the
moving electrons balances the electrostatic force.
B ev eE
x
·
whence
( )
2 2
2
LdB
V
Bd VL
V d
m
e ⋅
·
⋅ ⋅
≅
θ θ
.
The electron as a universal constituent of matter is supported by the fact that the same e/m is
obtained when i) different gases are in the tube, ii) different metals are used for the electrodes,
and iii) the electrons are released via the photoelectric effect rather than by heating the cathode.
e/m for the electron is many orders of magnitude smaller than e/m for the Hydrogen nucleus, so
the electron mass is many orders of magnitude smaller than that of an atom.
c. Millikan’s experiment
The charge to mass ratio of a particle has two properties mixed together. We’d like to get them
separately. For instance, what is the smallest possible charge a particle might have? We suspend
a small object, such as a droplet of oil or a tiny plastic bead, between two plates. We may apply
a voltage between the plates and observe the vertical motion of the droplet or bead, and do the
same with zero applied voltage.
39
Forces on the droplet:
D is the air resistance, C is the drag coefficient, and W is the weight of the droplet.
Without EField With EField
At terminal velocity Set EField such that v’ = constant
0 · −mg Cv
0 · ′ − − v C mg qE
v
mg
C ·
Substitute for C in the right hand equation,
0 ·
′
− −
v
v
mg mg qE
, solve for q/m.
,
`
.

′
− ·
v
v
E
g
m
q
1
Now, m is the mass of the droplet and q is the excess electric charge on the droplet. The volume
of the droplet can be obtained from Stoke’s “Law” for a sphere falling through a fluid medium.
From the volume and density of the droplet, we obtain its mass, m. We repeat the experiment for
many, many droplets and find that always q = ne, where n is an integer and e = 1.602x10
19
Coulombs.
2. Atomic architecture
If atoms are made of smaller building blocks, such as electrons, how are those blocks arranged?
We know, so far, that there are both positive and negative charges within an atom. The problem
is to arrange them in such a way that they stick together—the atom is stable.
40
a. Thomson
Atoms consist of a uniform, positively charged sphere throughout which are embedded tiny
negative particles—the electrons. This model gives a stable arrangement of +/ charges.
However, it fails to account for the observed emission & absorption spectra.
b. Rutherford
To determine the size of something too small to see, we can bombard that something with tiny
projectiles and observe how those projectiles are scattered. Rutherford (et al.) sent a beam of
heavy particles (alpha particles) into a thin gold foil. The result was the following:
Most α particles are undeviated, which means that the target gold atoms are not big mushy
balls. As the scattering angle, φ , increases, fewer α particles are scattered through that angle,
but not zero, and some even bounce backward, φ > π /2. We conclude that the target atoms are
several times more massive than the α particle and compact. Just how compact we can estimate
by using conservation of energy in a collision. In a direct, headon collision the α particle
reaches closest approach to the target atom when
r
e Ze
k v m
2
2
1
2
⋅
·
α α
.
Solve for that
) (
2
1
2
2
Z f
v m
e kZe
r ·
⋅
·
α α
. We find that
14
10
−
≈ r meters and that Z is roughly ½ the
atomic weight of the target atom. In other words, we find that the positive charge is confined to
a very tiny volume. However, the experiment does not tell us how the electrons in the target
atom are arranged within the atom’s structure. Rutherford proposed that either the electrons
were indeed mixed in the positive nucleus, or they orbited the positive nucleus. Just how the
positive nucleus could stay together was still a puzzle. Also still a puzzle was the emission &
absorption spectra of atoms.
41
c. The problem of atomic spectra
Certainly, an electron could orbit a positively charged nucleus just as planets orbit the Sun. After
all, the form of Coulomb’s “Law” is exactly the same as the “Law” of Universal Gravitation.
But, according to classical ElectroMagnetism, an accelerated charge emits radiation. That’s
how radio signals are generated, for instance. An electron in an orbit is certainly accelerated; it
should continuously emit radiation. Further, the emitted radiation should increase in wavelength
as the electron continuously loses energy and spirals inward toward the nucleus. What is
observed? i) Atoms do not emit continuous spectra nor ii) do atoms collapse—they are stable
objects.
During the latter part of the 19
th
century, many individuals measured the spectra of many
substances. Their findings are summarized by the following relation:
,
`
.

− ⋅ ·
2 2
1 1 1
i f
n n
R
λ
,
where n
i
and n
f
are integers and R is the Rydberg constant, R = 1.0973732x10
7
m
1
.
For Hydrogen:
Balmer series: n
f
= 2 and n
i
= 3, 4, 5, 6, . . .
etc. see the Table 4.1 in the text.
Note the spacing of the lines in each series, and that the series fall in different regions of the EM
spectrum. These are the experimental results that Bohr set out to explain in his model of the
atom.
3. The Bohr Model of the Hydrogen Atom
Bohr inferred certain properties of the atom from the observed spectra.
a. Assumptions/Postulates
i) The electron moves in stable circular orbits about the proton. The attractive force is the
Coulomb force.
ii) Only certain orbits are stable. In a stable orbit, the electron does not radiate, so the
energy is constant.
iii) Radiation is emitted when the electron makes a transition from one stable orbit to
another, and
hf E · ∆
.
iv) The angular momentum of the electron in its orbit is quantized, n mvr · . This
postulate arises in part from the idea of a standing deBroglie matter wave filling the
orbital circumference.
b. Energy levels of the Bohr Hatom
We use the assumptions mentioned above to see if we can reproduce the observed emission
spectra for Hydrogen. We have two threads: the conservation of energy and the quantization of
angular momentum.
42
The total energy is
r
e
k mv E
2
2
2
1
− · . Now, the v and r are not independent, since for a circular
orbit Newton’s 2
nd
Law says that
r
mv
r
e
k
r
2 2
· , or
r
e
k mv
2
2
· . Substitute this for mv
2
in E,
r
ke
r
ke
r
ke
E
2 2
1
2 2 2
− · − · .
This is the total mechanical energy of an electron in a circular orbit of radius, r. However, we
know that not all values of E are to be permitted, so at this point we invoke the quantization of
angular momentum, setting n mvr · , which leads to
2 2
2 2
2
r m
n
v · . At the same time,
mr
ke
v
2
2
· .
So we have two expressions for v
2
; set ‘em equal.
mr
ke
r m
n
2
2 2
2 2
·
Solve for r = r
n
2
2 2
mke
n
r
n
· , n = 1, 2, 3, 4, . . .
Finally, substitute this r
n
for r in the expression for E
,
`
.

⋅ − · − · − ·
2 2
4 2
2
2 2
2 2
1
2
2
2
n
e mk
mke
n
ke
r
ke
E
n
.
Notice the factor of
2
1
n
! These are the allowed energy states of the Hatom, according to the
Bohr Model, where m = mass of the electron, e = electric charge of the electron, k = coulomb
constant, and n is the principle quantum number. The lowest energy, and the smallest orbit, is
for n = 1. The radius of that n = 1 orbit is called the Bohr Radius, a
o
.
529 . 0
2
2
1
· · ·
mke
a r
o Å.
The corresponding lowest, or ground state energy is E
1
= 13.6 eV. The first excited state is for
n = 2, eV
eV
E 4 . 3
4
6 . 13
2
− ·
−
· , etc.
43
c. Hatom spectrum in the Bohr Model
Often we chart the allowed energy states on an energy level diagram:
The frequency of a photon emitted (or absorbed) in a transition between levels is
2 2
2
1 1
2
i f
o n n
h a
ke
h
E
f − ⋅ ·
∆
·
.
In terms of wavelength, λ ,
2 2 2 2
2
1 1 1 1
2
1
i f i f
o n n
R
n n
hc a
ke
c
f
− ⋅ · − ⋅ · ·
λ
.
The quantity
hc a
ke
o
2
2
is exactly equal to the experimentally derived Rydberg constant, R. So, the
Bohr Model of the Hatom can reproduce the observed emission/absorption spectrum.
d. Hydrogenic atoms
We may imagine extreme conditions wherein an atom is almost completely ionized, so that a
single electron orbits a nucleus with charge Ze. Then the Bohr Model would say:
Z
a
n r
o
n
2
· and
,
`
.

− ·
2
2 2
2
n
Z
a
ke
E
o
n .
An atom having a single electron orbiting a nucleus is called a hydrogenic atom.
4. Correspondence Principle
Classical, or preModern, Physics is not incorrect, only approximate and inaccurate for atomic
scale systems, just as it was for fastmoving systems. Thus, we would expect to be able to
extend quantumbased predictions to macroscopic systems and recover the classical result, again
just as the classical equations of motion were recovered for speeds small compared to c. This
44
expectation is called a correspondence principle. Such a principle serves as a check on
quantumbased reasoning and derivations.
E.g. In the case of a quantized oscillator (such as a mass vibrating on a spring), where
ω n E
n
·
and
m
k
· ω , on the macroscopic scale, we might have
kg m 1 ≈
and
m
N
k 1 ≈
, so
that
sec
1
rad
≈ ω
. The spacing between energy levels would be J x E
34
10 1
−
≈ ≈ ∆ . Similarly,
the spacing between adjacent energy levels of the Hatom approaches zero as the principle
quantum number, n, increases. To put it another way, in macroscopic systems, the level spacing
is too fine to be perceived by the human observer, so the energy appears to be a continuous
variable.
45
III. Quantum Mechanics & Atomic Structure (abbreviated)
We now seek a full treatment of particle dynamics in terms of matterwaves. That is, we want a
scheme of producing equations of motion.
A. Schrödinger Wave Equation—One Dimensional
1. Free Particle
A free particle is one subject to no external forces.
a. EinsteindeBroglie relation
ω · E and
k p ·
. A plane wave with this E and p would be written:
,
`
.

−
·
t
m
p
px
i
e y
2
2
,
where
p is the momentum, m is the mass,
m
p
E
2
2
· is the kinetic energy and
p
k · is the wave
number. An alternative form is
,
`
.

− +
,
`
.

− · t
m
p
px B t
m
p
px A y
2
cos
2
sin
2 2
. Which form is used
in a given case is a matter of convenience.
b. Free wave packet
A wave packet for a free particle is constructed of many plane waves:
( )
dp e p a dk e k a t x
t
m
p
px
i
t kx i
∫ ∫
∞ +
∞ −
,
`
.

−
∞ +
∞ −
−
· · Ψ
2
2
) (
2
1
) ( ) , (
π
ω
.
The transform gives the coefficients:
( )
∫
+∞
∞ −
−
Ψ · dx e x k a
t kx i ω
) 0 , ( ) ( .
c. Wave equation
This Ψ, a superposition of plane waves, satisfies the following differential equation:
Ψ
∂
∂
· Ψ
∂
∂ −
t
i
x
m
2
2 2
2
,
which can be verified by substitution. This equation is known as the Schrödinger Wave
Equation for a free particle.
2. Interpretation of the Wave Function, Ψ
a. Claim
The wave function contains all the information that can be known about a particle—its mass,
charge, energy, momentum, etc.
46
b. Proposed interpretation
The probability that the particle will be observed to be at a location between x and x+dx at time t
is given by
dx t x dx t x P
2
) , ( ) , ( Ψ ·
, where
Ψ Ψ · Ψ
*
2
and P(x,t) is the probability density.
To be realistic, Ψ must be continuous and single valued and must be normalized, since
1
2
· Ψ
∫
+∞
∞ −
dx
. That is, the particle must be somewhere on the xaxis. This proposed
interpretation is to be validated by experiment.
c. Solving for the motion
The problem, then, is to find Ψ(x,t), given Ψ(x,0), rather than x(t) given x(0), as in Newtonian
mechanics. We shall have to make the connection between
2
Ψ
and the physical motion of the
particle explicit subsequently. That is, later.
3. Particle Experiencing a Conservative Force
We draw an analogy with a wave propagating in a dissipative medium.
a. Schrödinger equation
t
i x U
x
m ∂
Ψ ∂
· Ψ +
∂
Ψ ∂
−
) (
2
2
2 2
,
where U(x) is the potential energy function for the external conservative force. The solution of
this equation may be easy or difficult, depending on the form of the U(x). Even so, we’re
assuming the potential energy function is constant in time.
b. Time independent Schrödinger equation
If the U is not a function of time, then the differential equation is separable, in the usual way.
We assume that
( ) ( ) ( ) t x t x φ ψ ⋅ · Ψ ,
. Then
( ) E
t
i
x U
x
m
·
∂
∂
· +
∂
∂
−
φ
φ
ψ
ψ
2
2 2
2
,
where E is the constant total energy of the particle. The space (x) equation to be solved is
ψ ψ
ψ
E x U
x
m
· +
∂
∂
− ) (
2
2
2 2
.
To go farther, we need to consider specific potential energy functions.
47
B. OneDimensional Potentials
1. Infinite Well or OneDimensional Box
a. U(x)
¹
¹
¹
'
¹
∞
∞
·
0
) (x U
L x
L x
x
< <
≥
≤
0
0
b. Conditions on ψ
¹
¹
¹
'
¹
·
) (
0
0
x ψ
ψ
L x
L x
x
< <
≥
≤
0
0
c. Solution
We have 3 regions in which the Schrödinger equation must be solved. Two regions are taken
care of already in this case, as ψ = 0 outside the potential well. Inside the well, U = 0, so the
particle is free.
ψ ψ
ψ
2
2 2
2
2
k
mE
dx
d
− · − ·
This is the equation for a plane wave, so for 0 < x < L,
) cos( ) sin( ) ( kx B kx A x + · ψ
.
To evaluate the coefficients, A & B, we apply the boundary conditions. We require that
ψ (0) · 0 and ψ (L) = 0.
0 ) 0 cos( ) 0 sin( 0 · ⇒ + · B B A
0 ) sin( ) cos( ) sin( 0 · ⇒ + · kL kL B kL A
, since B = 0.
If both A & B are zero, we have the trivial solution,
0 · ψ
.
d. Energy levels
Because sin(kL) = 0, there is a restriction on the energy of the particle in the well.
Evidently, kL = nπ , where n = 1, 2, 3, 4, 5, . . . Substitute for k in the total energy
2
2 2
2
2
2 2 2 2 2
2 2 2 mL
n
mL
n
m
k
E
π π
· · · , n = 1, 2, 3, 4, 5, …
Note: i) the quantized energy levels arise from the boundary conditions and ii) the lowest
possible energy is 0
2
2
2 2
1
≠ ·
mL
E
π
. This lowest possible energy is called the zeropoint energy,
even though it isn’t zero.
e. Normalization
The wave functions corresponding to the energy levels are
,
`
.

·
L
x n
A
n
π
ψ sin
. We evaluate A by
setting
∫
·1
2
dx ψ
.
∫ ∫
·
,
`
.

· 1 sin
2 2
2
dx
L
x n
A dx
π
ψ
Use the identity θ θ 2 cos 1 sin 2
2
− · .
48
( )
∫
· − ·
,
`
.

,
`
.

−
L
L
A
dx
L
x n A
0
2 2
1 0
2
2
cos 1
2
π
; solve for
L
A
2
· .
Because the wave function is zero outside the well, we integrate from 0 to L rather than t∞.
Finally, we have
,
`
.

·
L
x n
L
n
π
ψ sin
2
. [See Fig. 5.7 and 5.9 in the text.]
2. Expectation Values
a. Weighted averages
When averaging a list of values, we say
∑
∑
·
·
>· <
N
i
i
N
i
i i
p
A p
A
1
1
, where p
i
is the number of times the value A
i
appears in the list having N
different values.
b. Probability & expectation
Now,
2
Ψ
is the probability density, giving the odds that the particle will be observed to be in
the state described by Ψ(x,t). Suppose we make many observations of the position of the
particle. Then the average of our observations would be
∫ ∫
· >· < dx x dx x x
2
*
ψ ψ ψ
.
This is called the expectation value of x. The standard deviation of many observations of x is
( )
N
x x
x
i
∑
> < −
· ∆
2
N
x m x x x
x
i i
2 2
2 > < + > < −
· ∆
∑ ∑
2 2
> < − > < · ∆ x x x
,
where we could calculate
∫
>· < dx x x
2
2 2
ψ
.
c. particle momentum
49
We define the expectation value of the particle momentum as
dt
x d
m p
> <
> · < . For
macroscopic objects, this expression reduces to p = mv. Also,
2 2
> < − > < · ∆ p p p
.
50
C. ThreeDimensional Potentials
1. Threedimensional Schrödinger Equation
t
i r U
m ∂
Ψ ∂
· Ψ + Ψ ∇ −
) (
2
2
2
, where
2
2
2
2
2
2
2
x y x ∂
∂
+
∂
∂
+
∂
∂
· ∇
The solutions have the form ( ) ( )
t i
e r t r
ω
ψ
−
· Ψ
, .
2. Central Forces; polar coordinates
The Coulomb force is spherically symmetric, so it’s convenient to use spherical polar
coordinates.
a. Wave equation in polar coordinates
( ) ( ) ( ) ( ) r E r r U r
r r r r m
ψ ψ ψ
ϕ
θ
θ
θ
θ
· +
¹
'
¹
¹
'
¹
]
]
]
∂
∂
+
∂
∂
+
∂
∂
+
∂
∂
,
`
.

+
∂
∂
−
2
2
2
2
2
2 2
2 2
csc cot
1 2
2
For central potentials,
) ( ) ( r U r U ·
and we can separate the variables by assuming that
) ( ) ( ) ( ϕ θ ψ Φ Θ · r R
.
( ) ( ) ( ) 0 ) ( csc cot
1 2
2
2
2
2
2
2
2 2
2 2
· − +
¹
¹
¹
'
¹
¹
¹
¹
'
¹
]
]
]
∂
∂
+
∂
∂
+
∂
∂
+
∂
,
`
.

+
∂
∂
− r E r U r
r r r r m
ψ ψ
ϕ
θ
θ
θ
θ
Multiply through by
2
2
2mr
−
( ) 0 ) (
2
csc cot 2
2
2
2
2
2
2
2
2
2
2
· − −
,
`
.

∂
∂
+
∂
∂
+
∂
∂
+
,
`
.

∂
∂
+
∂
∂
ψ ψ
ϕ
θ
θ
θ
θ
ψ E r U
mr
r
r
r
r
Collect the terms depending on r and divide through by
ψ
.
0
csc cot 1
) ) ( (
2 2
2
2 2
2
2
2
2
2
2 2
· Φ
∂
∂
Φ
+ Θ
∂
∂
Θ
+ Θ
∂
∂
Θ
+ − −
∂
∂
+
∂
∂
ϕ
θ
θ
θ
θ
E r U
mr
R
r R
r
R
r R
r
We’ll have to solve this thing one piece at a time.
b. Angular momentum—the angular parts
51
C − · Φ
∂
∂
Φ
+ Θ
∂
∂
Θ
+ Θ
∂
∂
Θ
2
2 2
2
2
csc cot 1
ϕ
θ
θ
θ
θ
C is the separation constant.
Multiply by θ
2
sin
θ
ϕ θ
θ θ
θ
θ
2
2
2
2
2 2
sin
1 sin cos sin
C − · Φ
∂
∂
Φ
+ Θ
∂
∂
Θ
+ Θ
∂
∂
Θ
Separate again
Φ
∂
∂
Φ
− · + Θ
∂
∂
Θ
+ Θ
∂
∂
Θ
2
2
2
2
2 2
1
sin
sin cos sin
ϕ
θ
θ
θ θ
θ
θ
C
= m
2
, another separation constant.
Set
2
2
2
1
m · Φ
∂
∂
Φ
−
ϕ
, which equation has familiar solutions
ϕ im
e
t
· Φ .
Substitute this into the θ equation
2 2
2 2
sin
sin cos sin
m C · + Θ
∂
∂
Θ
+ Θ
∂
∂
Θ
θ
θ
θ θ
θ
θ
, rearrange
( ) 0 sin sin sin
2 2
· Θ − +
,
`
.

Θ m C
d
d
d
d
θ
θ
θ
θ
θ
.
This is a standard, “well known” differential equation—the Associated Legendre Equation. The
solutions are bounded and differentiable (the physical requirements) if
( ) 1 + · C
and
, 1 ,..., 1 , − + − − · m
.
We identify m with the angular momentum about the zˆ axis, which is quantized:
m L
z
·
,
t t t t · ,..., 3 , 2 , 1 , 0 m
The other constant is identified with the magnitude of the total angular momentum
( )
2 2
1 + · L ,
,... 3 , 2 , 1 , 0 ·
Note: ⇒ −
2 2
sin
m C θ combination of angular momentum about the xˆ  and
yˆ
axes.
Define:
≡
orbital quantum number and ≡
m magnetic quantum number.
52
c. Spherical harmonics
The “well known” solutions to the Associate Legendre Equation are the Spherical Harmonics:
( ) ( ) ( ) ϕ θ ϕ θ ,
m
Y
· Φ Θ
π 2
1
0
0
· Y
θ
π
cos
3
2
1
0
1
· Y
ϕ
θ
π
i
e Y
t t
⋅ · sin
2
3
2
1
1
1
etc. [see Table 8.3 in the text]
d. Radial equation
The radial part of the wave equation remains.
ER R r U R
mr
L
R
dr
d
r
R
dr
d
m
· + +
]
]
]
,
`
.

+ − ) (
2
2
2
2
2
2
2 2
.
The allowed energy levels are obtained from the boundary conditions applied to R(r); this will
give the principle quantum number, n. The details depend on the exact form of U(r). In the case
of the Hydrogen atom,
r
ke
r U
2
) ( − · .
e. Angular momentum vectors
L
z
is the projection of
L
on the zaxis.
Not only is the
L
quantized, but so is
the L
z
. For instance, for 1 · ,
2 2 2
2 ) 1 ( · + · L
, and
1 , 0 , 1 + − · m
, so
+ − · , 0 ,
z
L
. The
vector
L
precesses around the zaxis.
The condition
) 1 (
cos
+
· ·
m
L
L
z
θ
gives the allowed projections on the z
axis. For
1 ·
,
2
1
, 0 ,
2
1
cos − · θ
.
Fig. 7.7 in the text shows the case of
2 ·
.
53
D. The Hydrogen Atom
r
ke
r U
2
) ( − ·
So far we have
t i m
e Y r R t r
ω
ϕ θ ϕ θ
−
· Ψ ) , ( ) ( ) , , , (
. Given U(r), we have to find R(r). Notice
that many
m ,
combinations may apply to the same energy state, R(r)—degeneracy.
1. Radial Equation
ER R
r
ke
R
mr
L
R
dr
d
r
R
dr
d
m
· − +
]
]
]
,
`
.

+ −
2
2
2
2
2 2
2
2
2
The whole equation is multiplied by r. Then the second derivative term can be collapsed to
) ( ) (
2
) (
2
2
2
2
2
2 2
rR E rR
r
ke
mr
L
rR
dr
d
m
·
,
`
.

− + −
.
A standard method of solution is to try a power series:
∑
·
j
j
j
r a R
. The boundary conditions
will require that
0 ) 0 ( · R
and that 0 → R as
∞ → r
. The latter condition restricts the series to
be a finite polynomial with the highest
> ·n j
. This is what determines the allowed energy
levels. See Table 7.4 in the textbook.
2 2
4 2
1
2 n
e mk
E
n
− · , n = 1, 2, 3, 4, . . .
Commonly, we write E
n
in terms of the Bohr radius
2
2
1
2 n a
ke
E
o
n
− ·
.
It follows that the allowed orbital (angular momentum) states are =0, 1, 2, 3, . . ., n1.
2. Spectroscopic Notation
For a specified n, the allowed values of and
m
label states having the same energy, E
n
.
These states are said to form a shell; the allowed values of
m
for a specified form a
subshell. We still use the naming scheme created by the preModern spectroscopists who
measured atomic spectra in the 19
th
century. As shown in the following table, the letter K stands
for the n = 1 shell, while a lower case d stands for an = 2 subshell.
54
n(shells) symbol (subshells) symbol
1 K 0 s
2 L 1 p
3 M 2 d
4 N 3 f
5 O 4 g
6 P 5 h
We see that the quantum numbers
( )
m n , ,
arise from physical restrictions placed on the
mathematical solutions to the Schrödinger equation. Further, there is one quantum number for
each degree of freedom.
3. Probability Densities
) , ( ) (
, , ,
ϕ θ ψ
m
n m n
Y r R ·
a. Ground state
o
a
r
o
e
a
Y R
−
,
`
.

· ·
2
3
0
0 0 , 1 0 , 0 , 1
1 1
π
ψ
This function is spherically symmetric, since 0 · i.e., it’s an sstate. In fact, all states with
0 · are spherically symmetric. The probability density is
3
2
2
0 , 0 , 1
o
a
r
a
e
o
π
ψ
−
·
,
which is also spherically symmetric.
We define the Radial Probability Distribution, P(r) such that
dr r dr r P
2
2
4 ) ( π ψ ·
.
For
100
ψ
, o
o
a
r
o o
a
r
s
e r
a
r
a
e
r P r P
2
2
3
2
3
2
1
4
4 ) ( ) (
−
−
· · · π
π
.
Note that
2
2
) ( ) ( r R r r P ·
and that
1 ) (
0
·
∫
∞
dr r P
.
We can calculate the expectation value of r, the
distance of the electron from the atomic nucleus.
∫
∞
>· <
0
) ( dr r rP r
∫ ∫
−
∞
−
· · > < dr e r
a
dr e r
a
r r
o o
a
r
o
a
r
o
s
2
3
3
0
2
2
3
1
4 4
55
o o
o
o
s
a a
a
a
r 5 . 1
16
24
2
! 3 4
4 3
1
· ·
,
`
.

· > <
Notice: While r = a
o
is the most probable radius, the expectation value of the radius is <r> =
1.5a
o
, that is, averaged over a large number of observations of r.
b. First excited state
In the first excited state, n = 2. The orbital quantum number, , may be 0 or 1. If 1 · , then
m
= 1, 0, or +1. Therefore, there are 4 states with the same energy, E
2
. We say that the
degeneracy is 4fold. According to the spectroscopic notation, the 2s state is 0 , 0 , 2
ψ
; the 2p
states are 1 , 1 , 2
ψ
, 0 , 1 , 2
ψ
, and 1 , 1 , 2 −
ψ
.
2
200
ψ
2
211
ψ or
2
1 21−
ψ
2
210
ψ
4. Normal Zeeman Effect
a. Magnetic moments
Viewed in preModern terms, in circulating about the proton, the orbiting electron creates a
magnetic dipole field. The dipole moment is
µ
, having a magnitude of
jA · µ
, where j is the
timeaveraged electrical current and A is the area of the
closed orbit. If T is the orbital period, then
T
e
j
−
·
. On
the other hand, the magnitude of the orbital angular
momentum, according to Kepler, is
T
A m
L
e
2
· . The
magnetic moment vector becomes
e e
m
L e
m
T L
T
e
2 2
−
·
−
· µ
.
It’s convenient to define the quantity called the Bohr Magneton, thus:
Gauss
eV
x
Tesla
Jouls
x
m
e
e
B
9 24
10 788 . 5 10 274 . 9
2
− −
· · · µ
.
Notice the chargetomass ratio: e/m
e
. The quantity that appears in the magnetic moment is ½
the chargetomass ratio. For any charged particle, we define the geomagnetic ratio to be
m
q
2
,
where q is the particle charge and m is the particle mass. The zcomponent of
µ
, like L
z
, is
quantized:
m
B z
⋅ − · µ µ
.
56
b. Larmor precession
In an externally applied magnetic field, a magnetic dipole will experience a torque,
dt
L d
B
· × · µ τ
.
The
µ
vector precesses around an axis aligned along the
B
,
since the µ
⊥
dt
L d
and
B
.
dt LB
m
e
dt d L L d
e
θ τ ϕ θ sin
2
sin · · ·
.
e e
L
m
eB
L
LB
m
e
L
L d
2 sin
sin
2 sin
· · ·
θ
θ
θ
ω
This precession rate is called the Larmor Frequency.
c. Normal Zeeman effect
With no external Bfield, all the n = 2 states have the same energy, E
2
. In the presence of a
strong magnetic field, the interaction of the orbital magnetic dipole with the externally applied
magnetic field leads to a change in the energy. z
e e
L
m
eB
B L
m
e
B E
2 2
· ⋅ · ⋅ − · ∆
µ
, where we
have assumed that
z B B ˆ ·
. Thus, if E
2
is the state energy without the Bfield, then
m E E
L
ω + ·
2 is the energy
with the Bfield. Since
0 ·
m
,
1 t , 2 t , 3 t , . . ., tl , the
formerly degenerate energy
levels are separated by
L
m ω
t
. We call this lifting
the degeneracy. The higher the
value of n, the more
m
values
there are. The Normal Zeeman
Effect, then, is characterized by
the splitting of spectral lines into
sets of several uniformly spaced
lines in the presence of a strong magnetic field.
57
5. Fine Structure
a. Anomalous Zeeman effect
In addition to the uniformly split lines due to the normal Zeeman effect, there are often
nonuniform splittings of spectral lines. These are called the anomalous Zeeman splittings.
These are not accounted for by the orbital
µ
.
b. Stern –Gerlach experiment
Atoms passing through a nonuniform magnetic
field: any net magnetic dipole possessed by the
atoms will cause them to be deflected. The
observed result is that the atomic beam is divided
into two beams with equal but opposite deflections.
Interpretation: i) the effect is not due to the orbital
magnetic moment, else there would be either
1 2 + or zero spots on the screen and ii) the
deflections are due to a magnetic moment that has
only two possible values.
c. Electron spin
We propose that a magnetic moment is produced by the electron itself, visualized as spinning. In
analogy to orbital angular momentum, we define a spin quantum number, s, such that the number
of possible angular momentum zcomponents is 1 2 + s .
Since Stern & Gerlach obtained 2 1 2 · + s , we infer that for the
electron
2
1
· s
and that
2
1
t ·
s
m
. The zcomponent of the spin
angular momentum is s z
m S ·
, while
2 2
) 1 ( + · s s S . This S
2
is constant, so this thing called spin is an intrinsic property of the
electron as much as are its mass and electric charge.
The spin magnetic moment is
S
m
e
g
e
s
2
· µ
. The quantity g is
called the gfactor, which is a kind of a fudge factor. For electrons, the gfactor is found
experimentally to be
2 · g
. This value indicates that the electric charge is not uniformly
distributed in a tiny solid rotating sphere as our classical visualization depicts it.
d. Total magnetic moment of an electron
With these two contributions, the total magnetic moment of an electron in an orbit about a proton
is
( ) S g L
m
e
e
s
+
−
· + ·
2
µ µ µ
.
58
6. SpinOrbit Interaction
a. Potential energy of two magnetic dipoles
The orbital angular momentum gives rise to a magnetic moment. Call the Bfield due to this
moment
B , where
R
ev
R
vR e
B
o o
2 2
) (
3
2
µ µ
− ·
−
·
and
L
R m
e
B
e
o
2
µ
− ·
. With the electron in the
first Bohr orbit, R = a
o
.
L
a m
e
B
o e
o
2
µ
− ·
. This
B exerts a torque on the spin magnetic
moment, s
µ
:
B
s
× · µ τ
The potential energy contribution is
S L
a m
g e
B U
o e
o
s
⋅ − · ⋅ − ·
2
2
µ
µ , since
S
m
eg
e
s
2
−
· µ
. S
has two
possible orientations, so U may raise or lower the energy
level. What was once a single electron level becomes two.
This is called fine structure doubling.
b. Total angular momentum, J
The total angular momentum of the isolated Hydrogen atom is conserved: S L J
+ · . Let us
examine the possible values J
can have, based on the quantum restrictions on
L
and on S
.
By analogy (again), we introduce a new quantum number, such that
2 2
) 1 ( + · j j J and
j z
m J ·
, with m
j
= j, j1, . . ., j+1, j. What is the range of j? J
is the sum of
L
and S
, so
j takes on the values
2
1
t
for atomic electrons.
e.g. 2 · ,
2
1
t · s
then
2
5
2
1
2 · + · j
and
2
3
1
2
1
2 · − + · j
59
e.g. 4 · ,
2
1
t · s
then
2
9
2
1
4 · + · j
and
2
7
1
2
1
4 · − + · j
The number of m
j
values is 2j + 1. In terms of ,
2
1
t · j
, so there are
1
2
1
2 +
,
`
.

t
values
of m
j
—the projection of J
on the zaxis.
e.g.
2
1
0
2
1
t · ⇒ · ⇒ ·
j
m j
. [
2 1
2
1
2 · + ⋅
]
2
1
,
2
3
1
2
3
t t · ⇒ · ⇒ ·
j
m j
. [
4 1
2
3
2 · + ⋅
]
2
1
,
2
3
2
2
3
t t · ⇒ · ⇒ ·
j
m j
.
2
1
,
2
3
,
2
5
,
2
7
,
2
9
4
2
9
t t t t t · ⇒ · ⇒ ·
j
m j
. [
10 1
2
9
2 · + ⋅
]
Each m
j
level has slightly different energy since the angle between s
µ
and
B is different
fine structure.
e.g. the Sodium doublet
c. Spectroscopic notation
number for n
capital letter for orbital angular momentum
subscript for total angular momentum
e.g.
2
1
2
2
1
0
2
S
j
n
⇒
¹
¹
¹
¹
¹
'
¹
¹
¹
¹
¹
¹
'
¹
·
·
·
2
5
3
2
5
2
3
D
j
n
⇒
¹
¹
¹
¹
¹
'
¹
¹
¹
¹
¹
¹
'
¹
·
·
·
The usages of the 2 schemes of spectroscopic notation goes as follows: for orbital subshells we
use the lower case letters s, p, d, f, etc; for the energy states we use the capital letters S, P, D, etc.
60
E. Multielectron Atoms
Two effects are important: i) screening of the nucleus and ii) the exclusion principle.
1. Nuclear Screening
In a multielectron atom, each electron interacts not only with the atomic nucleus, but also with
every other electron in the atom. For instance, the twoelectron Helium atom:
The net effect is that electrons farther from the nucleus “see” a nuclear charge of something less
than Ze. The energy states are not simply the same ones found for the Hatom. This means in
practice that it is practically impossible to solve for the multielectron energy states exactly—
they have to be approximated to some degree.
2. Exclusion principle
It turns out that no two electrons within an atom can be in exactly the same quantum state. This
is a property of a class of subatomic particles called fermions. That is, no two electrons in an
atom can have exactly the same set of values for their quantum numbers. This has implications
for the electronic structure of multielectron atoms and the periodic table of elements. Namely,
no more than 2 electrons can occupy an atomic subshell, with
2
1
t ·
s
m
.
3. Electronic Configurations of the Elements
a. Shells & subshells
We envision the atomic energy levels to be labeled by quantum numbers n and 1s, 2p, 3s, 4f,
etc. These are called shells, since their probability densities are spherically symmetric around
the nucleus. The shells are divided into 1 2 + subshells, or orbitals, according to
m
. With
electron spin, each subshell has two levels. According to the exclusion principle, one electron
may occupy each level, so each shell may be occupied by up to
( ) 1 2 2 +
electrons.
In the atomic ground states, the subshells are filled in order of increasing energy. Commonly,
the outermost subshell is partially filled. These are the valance electrons.
b. Hund’s Rule
Each orbital (subshell) holds two electrons, spin up and down. However, within a shell, lower
energy is usually obtained if the spins are aligned, but in different subshells.
61
e.g. for Carbon 2p shell
this
↑ ↑
rather
than
↑
1 − ·
m 0 +1
This is Hund’s Rule: a shell is filled first with one electron in each orbital, spins aligned. Then
the second electron, with opposite spin, is placed in each orbital.
e.g. Oxygen & Fluorine 2p shell
Oxygen ↑ ↑ ↑
Fluorin
e
↑ ↑ ↑
c. Notation
The electronic configuration is written out by listing the occupied orbitals, and the number of
electrons in each orbital. See Table 8.2 for the ground states of the elements. e.g.,
atom config 1s 2s 2p 3s
H 1s
1
↑
He 1s
2
↑
Li 1s
2
2s
1
↑ ↑
Na 1s
2
2s
2
2p
6
3s
1
↑ ↑ ↑ ↑ ↑ ↑
As n increases, the spacing between levels decreases. So there are quirks in the order in which
shells are filled up.
e.g. see the elements 18 – 30. K is not [Ne] 3s
2
3p
6
3d
1
, but [Ne] 3s
2
3p
6
4s
1
. The 4s level is of
lower energy than 3d, so the 4s level fills before the 3d level is occupied.
e.g. worse, look at V, Cr, and Mn. The outer most shells are 3d
3
4s
2
for V; 3d
5
4s
1
for Cr; 3d
5
4s
2
for Mn.
Evidently, the energy levels are ordered thusly:
1s<2s<2p<3s<3p<4s~3d<4p<5s<4d<5p<6s<4f~5d<6p<7s<6d~5f. . . . where “4s~3d” means
these states have nearly the same energy.
62
Table of Contents TABLE OF CONTENTS..............................................................................................................1 I. RELATIVITY.............................................................................................................................2
A. Frames of Reference................................................................................................................................................2 B. Special Relativity......................................................................................................................................................5 C. Consequences of the Principle of Special Relativity.............................................................................................8 D. Energy and Momentum.........................................................................................................................................14 E. A Hint of General Relativity..................................................................................................................................19
II. QUANTUM THEORY...........................................................................................................21
A. Black Body Radiation............................................................................................................................................21 B. Photons....................................................................................................................................................................27 C. Matter Waves.........................................................................................................................................................31 D. Atoms.......................................................................................................................................................................38
III. QUANTUM MECHANICS & ATOMIC STRUCTURE (ABBREVIATED).................46
A. Schrödinger Wave Equation—One Dimensional................................................................................................46 B. OneDimensional Potentials..................................................................................................................................48 D. The Hydrogen Atom..............................................................................................................................................54 E. Multielectron Atoms.............................................................................................................................................61
1
I. A.
Relativity Frames of Reference
Physical systems are always observed from some point of view. That is, the displacement, velocity, and acceleration of a particle are measured relative to some selected origin and coordinate axes. If a different origin and/or set of axes is used, then different numerical values are obtained for r , v , and a , even though the physical event is the same. An event is a physical phenomenon which occurs at a specified point in space and time. 1. Inertial Frames of Reference
a. Definition An inertial frame is one in which Newton’s “Laws” of Motion are valid. Moreover, any frame moving with constant velocity with respect to an inertial frame is also an inertial frame of reference. While r and v would have different numerical values as measured in the two frames, F = ma in both frames. b. Newtonian relativity Quote: The Laws of Mechanics are the same in all inertial reference frames. What does “the same” mean? It means that the equations and formulae have identical forms, while the numerical values of the variables may differ between two inertial frames. c. Fundamental frame It follows that there is no preferred frame of reference—none is more fundamental than another. 2. Transformations Between Inertial Frames
a. Two inertial frames Consider two reference frames—one attached to a cart which rolls along the ground. Observers on the ground and on the cart observe the motion of an object of mass m.
The S’frame is moving with velocity v relative to the Sframe. As observed in the two frames:
2
∆t ′ In S we’d measure ∆ t. the a x = a x az = az . y y 3 . Then x = x ′ + v x ∆t ′ y = y ′ + v y ∆t ′ z = z ′ + v z ∆t ′ ∆t = ∆t ′ The corresponding velocity transformations are ux = dx dx ′ = + v x = u x′ + v x dt dt dy dy ′ uy = = + v y = u y′ + v y dt dt dz dz ′ ′ uz = = + vz = u z + vz dt dt ax = For acceleration du x dv = ax′ + x dt dt du y dv y ay = = a y′ + dt dt du dv az = z = az′ + z dt dt ′ . ∆ x’. a = a ′ .′ ∆x ′ In S’ we’d measure ∆ t’. and u x = . Also. ∆t b. and u x = ∆x . and ′ Note that for two inertial frames. we assume that ∆t = ∆t ′ . we assume that the origins coincide at t = 0. Galilean transformation Implicitly. ∆ x.
Write the 2nd “Law” in the S’frame. if m is constant. 4 . as they must for 2 inertial reference frames. That is.Example Sframe du dp F = ma = m = . so F ′ = m dt dt dt dt a = a ′ . where p ′ = mu ′ . dt dt S’frame du dp ′ du dv − = F . then transform the position and velocity vectors to the Sframe. Notice the technique. F ′ = ma ′ = =m . But u ′ = u − v .
the speed of sound is u . 1. in conformity with Newtonian or Galilean relativity. It uses interference to show a phase shift between light waves propagating the same distance but in different directions. in the S’frame the speed is u ′ . Particularly the measured wave speed was expected to depend on the frame of reference. We find (measure) that u = u ′ + v . Now. The source and the medium are at rest in the Sframe. wave motion was well understood. the ether must be very stiff. The classic experiment to detect the ether is the MichelsonMorley experiment. The whole apparatus (and the Earth) is presumed to be traveling through the ether with velocity. v . what is the medium in which light waves travel and in what reference frame is that medium at rest? That hypothetical medium was given the name luminiferous ether (æther). so it was expected that light waves would behave exactly as sound waves do. In the Sframe. MichelsonMorley Throughout the latter portion of the 19th century. A light beam from the source is split into two beams which reflect from the mirrors and are recombined at the beam splitter— 5 . experiments were performed to identify that preferred reference frame for light waves. Maxwell showed that these waves propagate through the vacuum with a speed c ≈ 3x10 8 m/sec. As a medium for wave propagation. it was established that light is an electromagnetic (EM) wave.B. b. Special Relativity MichelsonMorley a. Wave speeds Midway through the 19th century. yet offer no apparent resistance to motion of material objects through it. the frame in which the medium is at rest. We may identify a “preferred” reference frame. The questions were.
By measuring ∆ one could evaluate v . 6 . c 2 c2 . Take a look at the two light rays as observed in the ether rest frame. so that near the Earth’s surface the ether is at rest relative to the Earth. This null result is obtained no matter which way the apparatus is turned. preferred. For the forward light ray. rest frame for the propagation of light waves. so use the binomial theorem to simplify (1 − x ) −n n(n + 1) 2 = 1 + nx + x + 2! t≈ 1 v2 . The conclusion must be that either the “Laws” of electromagnetism do not obey a Newtonian relativity principle or that there is no universal. no v with respect to such an ether. the elapsed time from splitter to mirror to splitter is t2 = 2 v2 ≈ 1 + 2 c c The two light rays recombine at the beam splitter with a phase difference [letτ = ∆t c 2 1 v 2 c v 2 = ( t 2 − t1 ) = = . The sideward ray: The time required for the light ray to travel from the splitter to the mirror is obtained from v2 (ct ) = + (vt ) ⇒ t = 1 − 2 c c 2 2 2 −1 2 . there is no ether. c. 1 + c 2 c2 The total time to return to the splitter is twice this: t1 = 2t ≈ 2 v2 1 − 2 + = c −v c +v c c 2 1 v2 1 + . Expedients to explain the null result length contraction—movement through the ether causes the lengths of objects to be shortened in the direction of motion. etherdrag theory—ether is dragged along with the Earth. τ λ c 2 c2 λ λ c2 λ . Since ∆t However.forming an interference pattern which is projected on the screen.]: c ≠ 0 . no such phase difference was/is observed! So. the two light rays are out of phase even though they have traveled the same τ t distance. Now c >> v.
This is what Einstein did. This still implies that the “Laws” of electromagnetism behave differently under a transformation from one reference frame to another than do the “Laws” of mechanics. Principle of Special Relativity It doesn’t seem sensible that one “part” of Physics should be different from another “part” of Physics.’ b.’ When the speed of light is measured in the two reference frames. or anyway not exact. the Galilean Transformation is not correct. Evidently.Ultimately. Postulates of Special Relativity a. Let’s assume that they are not different. and work out the consequences. we assume the postulates are true. He postulated that ‘All the “Laws” of Physics are the same in all inertial reference frames. and work out the consequences. it is found that c ≠ c ′ + v . Second Postulate The second postulate follows from the first. ‘The speed of light in a vacuum is (measured to be) the same in all inertial reference frames. 7 . the expedients were rejected as being too ad hoc. 2. In any case. rather c = c ′ . it’s simpler to say there is no ether.
As shown below. 1. In the Sframe. Consequences of the Principle of Special Relativity Time Dilation a. S. One might say that an event is a point in spacetime (x. c. where 2 c t d ′ . d = d ′ + 2 . b.C. ∆x ′ = ∆y ′ = ∆z ′ = 0 . Two events may be separated by intervals in either space or in time or in both. c 2∆ t 2 c2∆ t′ 2 v 2∆ t 2 = + 4 4 4 c2 ∆t = ∆t ′ 2 c − v2 Solve for 1 2 = ∆t ′ 1− v2 . Time intervals Consider a kind of clock: We observe two events: i) the emission of a flash at O’ and ii) the reception of the flash at O’. Substitute for d .y. c Now let’s view the same two events from the point of view of another frame. the S’frame is moving to the right with speed v relative to the Sframe.t). The 2d ′ time interval between the two events is ∆t ′ = . ∆t ′ . and in terms of ∆ . c2 8 . and v. ∆x ≠ 0 . Events An event may be regarded as a single observation made at a specific location and time. The elapsed time is ∆t = 2d 2 . In this case.z.
In this example = v∆t = 0. The lifetime of a fastmoving particle is measured by noting how far it travels before decaying. of length L in its own rest frame.6 x10 −8 sec = 8. 111 in the text) The lifetime of a pion in its own rest frame is ∆t ′ = 2. Length Contraction a. moves to the right with a speed v relative to S. S’. S. 9 . we measure and t compute ∆ . such as a meter stick. 2. c. Consider a pion moving with speed v = 0.95 c ⋅ 8.33 x10 −8 sec = 23 .6 x10 −8 sec 1 − 0.33 x10 −8 sec 0.95 c in a lab—what will be measured as its lifetime in the lab? ∆t = ∆t ′ 1− v2 c2 = 2.6 x10 −8 sec. so that ∆x ′ = ∆y ′ = ∆z ′ = 0 . In practice.95 2 = 2. A second frame.example (prob. “Contraction” Consider an object.7 m. We observe two events: i) the point A passes the left end of the stick ii) the point A passes the right end of the stick.312 . Proper time The proper time is the time interval measured by an observer for whom the two events occur at the same place.
which is another way of saying only in terms of intervals. intervals are not the same for observers in different inertial reference frames. Proper length The proper length of an object is that length measured in the rest frame of the object. To the trackside observer at O. Simultaneity a. Synchronization We would like all clocks in a reference frame to display exactly the same reading simultaneously. Therefore. Yet both observers measure the same speed of light. smooth track. c. 3.As measured in the S’ frame. ∆x = L and v 2 . Flashes of light are emitted at the points C1 and C2 when the origins (O & O’) of the two frames coincide. To the observer on the train. L ′ = v∆t 1 − 2 = L 1 − 2 . the other observer stands beside the track. The contraction takes place in the direction of the relative motion. Lengths perpendicular to v are not affected. However. but can this be arranged? Only by the exchange of signals. Notice particularly that the stick is at rest in the S frame. the concept of two events being simultaneous has no absolute meaning. example: a train moving with constant velocity on a straight. b. One observer rides on the train. the flash emitted at C’2 is received before the flash emitted at C’1. as we have seen. 10 . ∆t ′ ∆t = v2 v2 In the S frame. the flashes are simultaneous. Nonsimultaneity Two events viewed as simultaneous in one frame will not be seen as occurring simultaneously in another frame. z coordinates and a “value of time” which we read off a clock located at that spatial location. however. rather there is a clock at every point in space. So for instance in the situation discussed above the width and thickness of the meter stick are still measured the same in both reference frames. Therefore. b. Spacetime Each event has associated with it four numbers: x. 1− 2 c c c An observer in the S’ frame observes the stick to be shorter (contracted) than does the observer in the S frame. y. There is no central universal clock. c. L ′ = v∆t ′ and ∆x ′ = 0 .
as measured in the S’ frame? In effect. we’ll be setting γ = 1 1− v2 .4. = x . then. x = γ ( x ′ + vt ′) γ = x ′ + vt ′ x On the other hand. we’ll have ∆t = t and ∆t ′ = t ′ . x = vt + γ ( x ′ + vt ′) = vt + x′ x′ γ . then. z = z ′ . S & S’ and assume that O = O’ at t’ = 0. 11 . Lorentz Transformation Now we wish to derive the transformation equations for the displacement and velocity of an object—the relativistic version of the Galilean transformation equations. these reduce to the Galilean transformation. ′ = x ′ + vt ′ x In the S frame. Two frames Consider two inertial reference frames. y = y ′ . t = γ t ′ + 2 x ′ c Notes: i) the inverse transformation is obtained by replacing v with –v. γ x′ Solve for t. ii) for v << c. vt = γ ( x ′ + vt ′) − γ v t = γ t ′ + 2 x′ c b. Transformation equations We have. In what follows. What is the xdistance from O to the point P. for relative motion along the xaxis: v x = γ ( x ′ + vt ′) . Set them equal. c2 a. Set ‘em equal. so ′ = γ also. as measured in the S frame.
There is this quantity. Transform to dt ′ dx −v u −v γ ( dx − vdt ) dt ′ = = = x the S frame. This is an extension of the invariance of lengths under a rotation of the coordinate d. The interval is invariant under the Lorentz Transformation. Transformation of velocities Since displacements and time intervals are transformed. a generalized displacement (call it s) which is the same in the two inertial reference frames. obviously relative velocities won’t add simply.c. That is. The interval between any two events in spacetime is ∆s 2 = ∆x 2 + ∆y 2 + ∆z 2 − c 2 ∆t 2 . u ′ = x dx ′ . Subtract the second expression from the first and collect the S frame on one side of the equal sign. 4vectors Suppose that when O = O’. the distance the light wave front travels in time t is r 2 = x 2 + y 2 + z 2 = c 2 t 2 . 12 . ∆ s 2 = ∆ s′ 2 . Measured in the S’ frame. In the S’ frame an object moves with constant velocity along the x axis. v 1 − v dx 1 − v u γ dt − 2 dx x c 2 dt c2 c While dy & dz are not contracted. the S’ frame on the other side. a flash of light is emitted from the origin O. In the S frame. either. ′s 2 s= 2 axes. u x and similarly for the y and z components. r − r′ = c t − c t′ 2 22 2 2 2 r − c t = r′ − c t′ 2 2 22 2 2 We see that the quantity (ict) “acts like” a component of displacement along a fourth axis. dt is still dilated. as measured in any two inertial frames. it’s r ′ = x′ + y ′ + z ′ = c t ′ 2 2 2 2 22 .
5c − (−0. then vu → 0 and u ′ = u − v .example: u A = −0.5c and u B = −0. then u ′ = cv v 1− 2 1− c c 13 . On the other hand. Therefore.8c . Note that when u < < c and v < < c . both as measured in the S frame. The S’ frame rides along with spaceship B.8c 2 1− 2 uA 1 − 2 0. if c2 u = c. uA − v − 0.5c c c Be careful with the directions of the velocities. v = u B .8c) c u′ = = = A v 0. v c 1 − c−v c = =c.
With this definition. Relativistic Energy a. pinitial = p final in all inertial reference frames. We require further that when v << c. Workenergy theorem (one dimensional) The work done by a force on an object changes its kinetic energy. 2 ∫ u2 1− 2 c Recall that udu = ∆K = up u2 − 1 u m 2∫ du 2 1− u2 c2 Look up the form ∫ dx in a math tables book. Conservation of Momentum p = γmu We define a relativistic momentum so that the two conditions above are satisfied. we recover the familiar Newtonian forms of the “Laws. This m is the rest mass—the mass measured by an observer at rest with respect to the object.” This latter requirement is called a Correspondence Principle. This quantity should be the same in all inertial reference frames. a +bx 14 . ∆ = ∫udp K ∆K = up u2 1 u2 u1 u2 u1 − u2 u1 ∫ pdu mu du ∆K = up u − du 2 . thus ∆K = W12 = ∆K = ∆K = ∫ t1 t2 x2 x1 ∫ Fdx . 2. Energy and Momentum We require that all the “Laws” of Physics be the same in all inertial reference frames.D. x2 x1 ∫ dt dx dp dx dt dt dt dp Integrate by parts. What are those “Laws”? 1.
The total relativistic energy is E = K + mc2 + V. if any. if we started from rest. 15 . we − mc 2 . then u1 = 0 and u2 = u and define the relativistic kinetic energy to be K= mc 2 1− u c2 2 ∆K = mc 2 1− u c2 2 − mc 2 . m = 0 and E = pc. The quantity mc2 is called the rest energy. where V is the potential energy. E 2 −m2c 4 = c 2 p 2 E 2 = c 2 p 2 + m2c 4 For photons. If V = 0. because it’s independent of u. Therefore.∆K = up u2 1 u u2 2 1 − 2 m c − 1 2 − 2 c 2 u 1 2 u 1 u mu 2 u2 ∆K = + mc 2 1 − 2 2 c 1−u 2 c mu ∆ = K u 2 u + mc 1− 2 − mu 2 2 u c2 2 2 = ∆ mc 2 1−u 2 u c 1 Now. then E = K + mc 2 = γmc 2 . Energymomentum relation Take a look at the quantity (V = 0) 2 2 m2c 4 m 2 c 2u 2 m u E 2 −m2c 4 = −m2c 4 = =c2 2 2 u u u2 1 − 2 1− 2 1− 2 c c c . b.
3. m.511 MeV . Sometimes. we define the relativistic force component mu x px = dp x to be Fx = . They have equal masses. 16 .11 x10 −31 kg (3 x10 8 m / sec ) = 8. At the other dt du F = .60x1019Joules. dt 1− 2 c Let’s say the motion and force are entirely along the xdirection. we want to recover the classical result when u << c. The rest energy of an electron is 2 mc 2 = 9. mass is expressed in terms of MeV/c2 so that the electron mass is 0. Thus 1 eV = 1. that as u → c. Also. Force We want the “Laws” of Mechanics to be invariant under the Lorentz Transformation. du F u2 = 1 − 2 dt m c 3 2 du → 0 .20 x10 −14 J = 0. momentum is expressed in terms of MeV/c. b. An electronvolt is the energy gained by an electron upon being accelerated through a one Volt potential difference. d m u F = 2 dt 1 −u c2 m du d 1 = +m u 2 dt u 2 dt 1 −u 1− 2 c c2 F= m 1− u 2 du u2 1 + mu − 1 − 2 dt c 2 2 1 − u c2 −1 2 −3 2 2u du − 2 c dt −3 2 c2 u2 + 2 c 3 2 du F =m dt u2 1 − c2 du dt 1 F = m u2 1 − 2 c Solve for the acceleration. when u << c. Often. Relativistic Mechanics a. where u2 . Similarly. dt m The result is. but it’s understood to still be there. extreme. Let’s say that one ball is initially at rest while the second ball has momentum po and energy Eo before the collision. So. since pc = units of MeV.c.511MeV/c2. no matter how large the applied force. the c2 is dropped.511 x10 6 eV = 0. Units of massenergy It is convenient to express energy in units of electronvolts (eV). Collisions—conservation of momentum Consider the collision of two billiard balls.
But. 1 2 2 Eo − m 2 c 4 = E 2 − m 2 c 4 cos θ c c Conservation of energy allows us to eliminate E. p 2 = 323 . m1c 2 = m2 c 2 = mc 2 = 139. the cosine of the scattering angle. In the x direction. p o = 2 p cos θ . The total energy is E o = 921 MeV + 352 MeV = 1273 MeV The quickest way to obtain the magnitude of the incident momentum is to use the law of cosines: 17 . c c E o = E1 + E 2 = 2 p1 c 2 + m 2 c 4 + 2 p2 c 2 + m 2 c 4 The energy and momenta are conserved. hoping to identify it. m. since it was given that Eo + mc 2 = 2 E . E o ≈ mc 2 and therefore 2mc 2 1 = ⇒ θ = 45 o . Substitute for po and p using E2 = p2c2 + m2c4. Knowing the momenta and masses of the decay products. as Eo >> mc2. as shown. 2 2 4mc cos θ → 1 ⇒ θ → 0 o ! cosθ ≈ c. cosθ = (E 2 Eo − m 2 c 4 o + mc2 ) 2 − 4m 2 c 4 = )( ( E + 3mc )( E o o 2 (E + mc2 Eo − mc2 o − mc 2 ) ) cosθ = E o + mc 2 Eo + 3mc 2 In the classical limit. while mc2 is the rest energy of the first (target) ball. p1 = 910 MeV MeV . E. At the same time.After the collision. Momentum and energy are conserved. It’s an elastic collision. Decay of a highenergy particle An unidentified highenergy particle is observed to decay into two pions ( π mesons).6Mev . Keep in mind that Eo is the relativistic total energy of the second ball. and mass. we determine the mass of the incident particle. both balls have the same energy. we solve for cos θ .
781 MeV.781 MeV = 939 . the incident particle was a ρ meson.511 MeV + 0.28 MeV + 0.57 MeV Notes: i) The rest energy of the antineutrino is too small to bother with. 1− 2 c 2 mo c 4 u = 1− = 0 . The total final energy is E f = m p c 2 + me c 2 + K = 938 . 18 . ii) Keep in mind the rounding of numbers and significant digits when substituting numerical values into the formulae. iii) Notice that mn ≠ m p + me . For instance. A portion of the neutron’s rest energy has been converted into kinetic energy. Massenergy equivalence When we speak of the total energy being conserved that includes the total rest energy. The three product particles are observed to have total kinetic energy of K = 0.8 2 c Eo mo c 2 = 2 2 E o − p o c 2 = 765 MeV d. The initial energy is just the rest energy of the neutron. an electron and an antineutrino. What was its speed before it decayed? Well.2 2 p o c 2 = p12 c 2 + p 2 c 2 − 2 p1 p 2 c 2 cos θ = 1034229 MeV 2 p o c = 1017 MeV Now that we have the total energy and the kinetic energy. 2 mo c 4 2 E = the total energy is also o u 2 . so solve that for u. Ei = 939. consider the decay of a neutron that is initially at rest. n → p + e +ν The neutron decays into a proton. the mass is obtained from 2 2 2 E o = p o c 2 + mo c 4 Evidently.57 MeV.
experiment has shown that it does. at a constant rate. It follows that the force of gravity must affect a beam of light just as it affects the motion of a massive projectile. light has no mass. relative to us. know that this second elevator is resting on the surface of a planet. Pendula would swing back and forth just the same. then the person inside will have no perception of the elevator’s motion. Can the same be said for reference frames that have a relative acceleration? a. regardless of its acceleration relative to another frame. as omniscient external observers.] Contrast this situation with that of another person standing in a similar elevator. The Postulate of General Relativity asserts that the “laws” of physics have the same form for observers in any frame of reference. [Keep in mind: the person gets no information from any source outside the reference frame of the elevator. The light follows a curved path inside the elevator. A Hint of General Relativity Equivalence In Special Relativity it is asserted that all inertial reference frames are equivalent—the “laws” of physics are the same in all inertial reference frames. a o . The person in this elevator also feels the floor pressing upward on his or her feet.E. we observe a closed “elevator” which is accelerating. also has no perception of the elevator’s motion. The point is that there is no experiment that either of the persons inside the elevators could perform that would distinguish between the two situations. We. Elevator Recall the past discussion of a person standing in an elevator. If the elevator moves perfectly smoothly and there are no floor indicator lights. But. Indeed. We have seen that an accelerated frame is equivalent to one in a gravitational field. Nearby. but this elevator is simply resting level on the Earth’s surface. 1. etc. projectiles would follow the same kinds of arcs. 19 . except for feeling perhaps the elevator floor pressing upward on his or her feet. Light and gravity Imagine ourselves as observers far from any source of gravitational force. b. and that what the person inside is experiencing is the gravitational force exerted by that planet. No experiment done in one frame can detect its uniform motion relative to another frame. A person standing inside the “elevator” sends a series of light pulses toward one wall—he or she and we see the light pulses dropping toward the floor as they approach the wall.
we can nonetheless mathematically transform the “laws” of physics into versions of the same mathematical form that do not include gravity yet which make equally accurate predictions of the motions of particles and of light beams. Objects and light beams move always in straight lines. If the “elevator” is in a gravitational field. What Einstein did was to formulate such a version of the “laws” of motion. However.2. we would say that a mass. slowing binary neutron stars 20 . exerts a gravitational force on another mass. a person in an “elevator” cannot determine whether his or her “elevator” is in the gravitational field of a planet or is being accelerated at a constant rate by. Curvature Classically. say rocket motors. Predictions of General Relativity: Precession of orbits—Mercury Gravitational redshift—time runs slower in intense gravitational field Gravitational lensing—light paths curved Gravitational waves—ripples in space time(?). such as a moon or a person. such as a planet. but the presence of mass at any location curves spacetime to a degree proportional to the amount of mass that is present. Empty spacetime is flat. but in a curved spacetime.
Black Body Radiation Equilibrium Between Matter and Radiation a. The radiation is said to be in thermal equilibrium with the walls of the oven. Quantum Theory A. To. Ultimately.II. Conversely. where J is the power radiated per unit area per unit frequency. The observed spectrum of radiation emitted by a black body looks qualitatively like this: c.T ) = Ef Af . The black body is not the oven as a whole. Emissivity From thermodynamics (Kirchhoff) the power radiated by a body in thermal equilibrium with radiation is expressed J ( f . Because the opening is small. Model for a black body One physical model for an ideal black body is a small opening in the wall of a heated cavity. but the opening in the oven wall.0 for all f. any light ray that exits through the opening will have reached equilibrium with the interior walls. A f =1. For a black body. Af is the fractional absorption of the body for radiation of frequency f. maintained at a constant temperature. isotropic and unpolarized. EM waves bounce from wall to wall. b. 1. the radiation is rendered homogeneous. Inside. 21 . Notice that the substance of which the body is made is not important. having bounced off the walls many times. being absorbed and reemitted over and over. a light ray entering through the opening is very unlikely to bounce back out again. Ef is the emissivity or intensity per unit frequency of the radiation emitted by the body and . Thermal equilibrium Imagine a closed oven. A thermometer placed in the center of the oven will stabilize at a temperature T = To .
Let N(f)df be the number of modes between f and f+df. c where u is the energy per unit volume per unit frequency. Boltzmann derived this result from Maxwell’s equations. T ) = Af 3 e where A and β are constants. Wien’s exponential “law” fits well near the peak.T ) = 4 J ( f . RayleighJeans “Law” Wien’s exponential “law” u( f . T u ( f . Emissivity The total emissivity is obtained by integrating Efdf. σ = 5. at f max . For nonm2 K 4 black bodies. −β ⋅ f b. Wien’s displacement “law” c f max ⋅ T = 2. But. Subsequently. E = ∫ E f df 0 ∞ This quantity was found experimentally by J.T ) . As derived from thermodynamics and Maxwell’s equations. StefanBoltzmann “Law” a. λmax ⋅ T = 2.2. When tested by experiment.898 x10 −3 m ⋅ K . Rayleigh’s approach Rayliegh proposed that the energy density be expressed as the product of the number of standing wave modes in the cavity and the average energy of each mode. where a < 1. a. Experimentally. or 3. uf d = N ( f )Ed f We need to obtain expressions for N(f) and for E . Stefan to be proportional to T4. In one dimension: 22 . this expression fails at long wavelengths. Picture standing waves in a cavity. b.898 x10 −3 m ⋅ K . E = aσT 4 . The proportionality −8 constant is called the StefanBoltzmann constant.67 x10 E = σT 4 W or Wm2K4.
the probability that there will be a mode of energy. In other words. at temperature T. ny and nz are positive integers.We imagine the whole volume of the cavity occupied with standing EM waves. consider a cubical box of side L. Classically. the xcomponent of the Efield satisfies the wave equation ∇2 E x + k 2 E x = 0 . we count the number of kpoints lying in a spherical shell of radius k and thickness dk. 23 . 2 2 The quantity k2 is like the square of a radius in kspace: k 2 = k x + k y + k z2 . Similarly. Inside the box. in the cavity is given by the Boltzmann distribution. k x = x . of many different frequencies. with the electric field vanishing at the walls. the density of states. P( E ) = e The average energy per mode is therefore ∞ −E k BT E = ∫ Ee 0 ∞ 0 −E k BT dE = ( k BT ) 2 k BT ∫e −E = k BT k BT dE As for N(f). only discrete points L in kspace designate the allowed energy modes in the cubical cavity. If we assume that E x = u ( x )v( y ) w( z ) . The radiation is in equilibrium with the walls of the cavity. The one for u(x) is d 2u 2 + kx u = 0 . v( y ) = vo sin k y y and w( z ) = wo sin k z z . E. dx 2 which has the solution u ( x ) = u o sin k x x . So. Since we must have n yπ nπ standing waves in the box. where the nx. then we get three separated equations. k y = L L nπ and k z = z .
T )df = N ( f ) E df = λ Compared with the observed black body spectrum. Planck’s “Law” 24 . there are two perpendicular polarizations for each mode. π L 3 where V = L3. 4. This diverges for small wavelengths (the ultraviolet catastrophe). Finally. dk = V π2 kc N( f ) 8πf 2 df In terms of frequency.π We see that each point occupies a volume so the number of points in the shell is L 1 4πk 2 dk Vk 2 dk 8 N (k )dk = = 3 2π 2 . c3 Alternatively. What do we have so far? We have regarded the range of allowed energies for a standing wave in the cavity to be a continuous variable. so the number of modes per unit volume (the density of states) is N (k ) k 2 dk . the energy density in terms of wavelength is 8π u (λ. The result obtained is proportional to one over the fourth power of the wavelength. T )dλ = 4 k B Td λ u ( f . the RayleighJeans “law” is seen to diverge as λ → 0 . . df = 3 2π V c At last the energy density is 8πf 2 k B Tdf . since f = .
a. the denominator. . No other energy values are allowed. . to c3 25 . Quantized energy modes Rather than visualize standing EM waves inside a cavity. rather than continuously. consider the atoms that form the walls of the cavity. n =0 n =0 − n hf −n hf d d 1 k BT k BT e = −∑ ne = ∑ −hf hf Notice that hf n . k BT Firstly. Postulate: En = nhf where n is a positive integer. substituting this into E . Let’s assume that the energies of these oscillators can change only in discrete steps. Therefore. ∑e n =0 ∞ nhf − k BT = 1 1−e − hf k BT . N ( f ) = obtain. . . . The average energy per vibration mode is a discrete sum E = n =0 ∞ ∑ En e ∑e n=0 − ∞ − En k BT En . we have n 1 − e k BT d d k T k T B B −hf E = −hf 1 − e k BT d 1 hf −hf d 1 − e k t B E = hfe −hf −hf k BT = −hf hf hf −hf 1 − e k BT −e −hf 1 − e −hf k BT k BT 2 k BT k BT 1 − e = e k BT −1 This result is multiplied by the number of modes having frequency f. 8πf 2 . This follows from the series of the form ∑r n = 1 − r n =0 ∞ 1 with r =e − hf k BT . . Secondly. −hf −nhf −hf −nhf ∞ ∞ k BT k BT E = 1 − e k BT ∑ nhfe = hf 1 − e k BT ∑ ne . These atoms vibrate and absorb or emit EM waves.
Fitting Planck’s formula to the observed black body radiation yields a value for Planck’s constant. −1 → 0 . therefore the probability that a high frequency or short 26 . ii) For high f.b. T ) = 8πf 2 ⋅ c3 hf hf = −1 8πhf c 3 e hf 3 e k BT k BT . Planck’s distribution formula u( f . the 1 hf e k BT wavelength mode is occupied or present is very low.626x1034J sec. En = nfh. −1 What do we have? i) Assume that oscillators or standing waves are limited to discrete values of energy. h = 6. iii) An oscillator that emits energy can change its energy only in steps of ∆E = nhf . where f is the vibration frequency of the oscillator.
B. the photoelectrons have a distribution of kinetic energies. 1. called the work function. Interpretation: Increasing the intensity of the incident radiation does not increase the left over kinetic energy of the photoelectrons. Work function Finding: Kmax is proportional to the frequency. We can evaluate the maximum. Photons Photoelectric Effect a. f. A certain amount of energy. Finding: Kmax is independent of the incident intensity. of the kinetic energy distribution by applying a voltage. is required to liberate an electron from the metal. Kinetic energy When a metal surface is exposed to intense monochromatic EM radiation. Vs. Kmax = eVs. while the photocurrent is proportional to the incident intensity. only the number of electrons ejected from the metal. Kmax. of the incident radiation with an fo below which no photoelectrons are produced (Kmax = 0). b. electrons are expelled from the metal. large enough to stop the fastestmoving electron from escaping. Once liberated. 27 .
the emitted wave has a Dopplershifted frequency. 2. Either a photon is absorbed entirely. Absorption of a classical EM wave Suppose a continuous EM wave (frequency fo) is incident on a free electron. This is not what is observed. 28 . b. the light is absorbed in discrete portions. Compton Effect a. The longer the electron is exposed to the incident radiation. light is emitted in the form of one or more discrete photons. increasing the intensity only liberates more electrons. Likewise. each one absorbing one hf and no more.Interpretation: K max = eV s = hf − φ . Since the electron is now moving. but consists of discrete. The classical prediction is that the electron will experience acceleration causing the electron to oscillate transversely and to move in the direction the light wave is traveling. f is the frequency of the incident radiation and h is Planck’s constant. ∆E = hf . If the incident frequency is such that hf ≤ φ . or not at all. then no photoelectrons are produced. only. localized wave packets. The accelerated electron in its turn emits a new EM wave. since it influences the electron’s acceleration. The intensity of the incident radiation also influences the Doppler shift. where φ is the work function of the metal. That is. We conclude that EM radiation is not a continuous wave form. the faster it translates and the greater is the Doppler shift. If hf < φ . Collision between a photon and an electron Consider a collision between an xray photon and a stationary free electron. if hf > φ . then Kmax = 0 and no electrons escape from the metal. called a photon.
c c λ 2 2 On the other hand. thusly: λ′ − λ = h (1 − cos θ ) . Usually. both energy and momentum are conserved. p = E hf h = = . Theoretical treatment as a collision As a collision between two particles. θ . if not equal to c. (hf − hf ′ + m c ) 2 4 2 e hf ′ 2 hf 2 h 2 ff ′ 2 4 = c 2 + − 2 2 cos θ + me c c c c ′ 2h 2 ff ′ + 2hfm e c 2 − 2hf me c 2 = −2h 2 ff ′ cos θ 29 . me c c. the energy of the electron is also E e2 = p e c 2 + me c 4 . Energy E + me c 2 = E ′ + E e hf + me c 2 = hf ′ + E e momentum components p = p ′ cos θ + p e cos φ 0 = p e sin φ − p ′ sin θ The first step is to eliminate φ from the momentum component equations. since the photon is certainly moving at a speed close to. what is observed is that the frequency. It is necessary to use the relativistic forms of energy and momentum. p = p ′ cos θ + p e p′ 1− p sin θ e 2 Square both sides and solve for pe2 = p′ 2 + p 2 − 2 pp′ c oθ s . Substitute for Ee and pe. me c The quantity h = 0.0243 Å is called the Compton wavelength of the electron. the effect is expressed in terms of the shift in wavelength.Qualitatively. of the scattered photon depends only on the scattering angle. For the photon. f ′ .
− 2hme c 2 ( f − f ′) = 2h 2 ff ′(1 − cos θ ) f − f′ 1 1 h (1 − cosθ ) = − = ff ′ f ′ f me c 2 λ′ − λ = h (1 − cos θ ) me c h This Compton shift formula exactly matches the observations. then. We conclude. 30 . that a photon behaves like a particle having relativistic energy hf and momentum λ .
Using these quantities. Waves in one dimension 2πx y = A cos − 2πft and v p = λf . define for any particle a wavelength λ = h/p. Beats Superimpose two waves: y = y1 + y 2 = A cos( k1 x − ω1t ) + A cos( k 2 x − ω 2 t ) . Matter Waves We find that light is quantized and may be regarded in some circumstances as being particles of zero mass. ω y = A cos ( kx − ωt ) and v p = . momentum h/λ . Group velocity A particle occupies a limited volume. ω +ω2 k + k2 1 y = 2 A cos { ( k 2 − k1 ) x − (ω 2 − ω1 ) t} ⋅ cos 1 x− 1 2 2 2 t . deBroglie wavelength For a photon. We accomplish this by superimposing many waves of differing wavelengths and amplitudes and phases. a. a frequency is defined as f = E/h. v 2. If the relativistic expressions for E & p are used. Phase velocity of a wave The phase velocity of a wave is vp = fλ = E/p. p = h/λ . then we get a phase velocity for a massive particle vp = mc 1− v 2 2 1− v c 2 2 c2 mv c2 = . Some persons use the quantum point of view exclusively. In a similar vein. λ We define the angular frequency. ω = 2π f and the wave number. so if we are to represent it with a waveform. deBroglie’s Postulate a. Further.C. k = 2π /λ . the waveform amplitude must be nonzero only in a limited region of space. k b. [Note: cos(a) + cos(b) = 2cos(½ (ab)∙cos(½ (a+b). b. if E is the total relativistic energy of the particle. and energy hf.] 31 . Might it be useful to investigate whether nonzero mass particles can be treated as having wave properties? 1. where p is the momentum (magnitude) of the particle.
then the medium through which the waves are propagating is said to be dispersive. The wave packet would be constructed by a superposition of harmonic waves having wavelengths centered on λ 0. ∆k ∆k 2 +k dv p ko dk . The timevarying amplitude is A ′ = 2 A cos ( ∆kx − ∆ωt ) . Wave packets The beating waveform still extends to ± ∞ in x. With sound waves. e. and having a range of wave numbers centered on a ko. The mathematics of the superposition will be explored in paragraph 4. For the time being. We can construct a wave packet that is nonzero only in a small region by superimposing many waves having different amplitudes. Dispersion If vp = vp(λ ). c. The individual harmonic waves travel at different speeds.We have a traveling wave whose amplitude is not constant. since ω = kv p . the regular rises and falls of the amplitude are known as beats. from the form of A′ . That combination is constructed only of two waves having the same amplitude but slightly different frequencies or wave numbers. Its mass is m and it is moving uniformly with speed v. so the wave packet or wave group spreads out with time. The envelope also travels at a speed called the group velocity. The phase velocity is vp = fλ = E/p. y = A′ cos ( k ′x − ω ′t ) . where ω + ω2 k + k2 k′ = 1 and ω ′ = 1 . Application to a massive particle We consider a massive particle (in this context. d. This 2 2 A′ is also known as the envelope. such as the electron. We postulate that the motion of the particle can be modeled by a traveling wave packet with frequency fo = E/h and wavelength λ o = h/p where E is the total relativistic energy and p the total relativistic momentum of the particle. Putting E in terms of p and p in terms of the wave number k yields [ E = p2 h and p = ] 2m 2πk 32 . ∆k ⋅ ∆x = 2π and ∆ω ⋅ ∆t = 2π . v g = ∆ω Evidently. massive means having a nonzero mass). we are concerned with the group velocity of the wave packet: vg = dω =v p dk k o ko 2 = ∆ω .
We count the number of electrons that are scattered at an angle ϕ from the incident direction. we obtain the group velocity dω =v p dk k o 2 ko dk mc vg = c 1 + ko ( − 2) mc 13 c k o + ko 2 2 mc 1+ k o 2 2 vg = c mc 1+ k o = c2 vp ko . Previously. mc v p = c 1+ k vg = 2 . When a monochromatic light beam is incident on a diffraction grating. +k dv p ko From this expression. 3. Electron diffraction Consider a monoenergetic beam of electrons incident on a crystal lattice. Therefore. entirely understood in terms of the constructive and destructive interference among the scattered light waves. where = h 2π . we saw that the phase velocity also equals c2/v. a characteristic interference pattern is observed. The electrons will be scattered from regularly spaced centers. a. 33 . the group velocity of the wave packet coincides with the velocity of the massive particle: vg = v. DavissonGermer experiment How might wavelike behavior of massive particles be observed? One of the prominent characteristics of waves is the fact that they interfere with each other to form interference patterns.
34 . So check how fast the electrons are moving.We do not observe either a uniform distribution with scattering angle. we observe a distribution of scattered electrons something like this: b. 511 MeV. That is MeV 2 ⋅ 0. The kinetic energy is K = γ mc2 – mc2. nor a sharp peak at ϕ = 0 and no particles elsewhere.67Å. The question is. then the peak at ϕ = ϕ max occurs when d ⋅sin ϕ = λ .65Å. Specifically. [We are imagining that the rows of atoms forming the surface of the crystal correspond to the closely spaced lines of a grating. Therefore.15Å whence we obtain λ = 1. 4. Thus γ – 1 = 0. It appears that the deBroglie postulate has some physical reality. Beyond the slits is a detector. We have K = 54 eV and mc2 = .0001. Uncertainty and probability Consider a simplified electron diffraction experiment: a monoenergetic beam of electrons impinging on two narrow slits. does this wavelength correspond to the deBroglie wavelength of such an electron? Firstly. it will be easier if the relativistic formulae are unnecessary. The deBroglie wavelength is K p = 1. The electrons all have the same kinetic energy and the same velocity.511 2 ⋅ 54eV c close enough in view of the rounding used in the calculation. where d is the spacing between neighboring atoms in the crystal. Rather.136 x10 −15 eV ⋅ s λ= = p = 2m . h 4. for 54 eV electrons impinging on a Ni crystal. Interpretation If this result is interpreted as wavelike interference. We can use the classical expression K = p2/2m. which can be moved along the xaxis.] We might solve for the wavelength: λ = d∙sin(ϕ max). ϕ max = 50o and d = 2.
a. not the superposition of two singleslit distributions. the interference pattern is obtained. For a single slit we would obtain. with either one slit or the other open. such that Ψ equals that probability. Define a wave function. we obtain. This parallels the definition of intensity for light waves. the detector counts electrons one at a time.The observed result: Note that at a specific location. If both the slits are open while electrons are being counted. open however just one at a time in succession. After counting for a “long” time at several xvalues. we would observe a superposition of the singleslit distributions. The number of particles we expect to count in the interval x’ to x’+∆ x is proportional to the probability that an electron will 2 be counted at x lying between x’ and x’+∆ x. and being counted by the detector. passing through them. Probability We have a stream of many electrons incident on the double slits. so the intensity being measured is I(x) in particles per minute. x. The detector counts the number of electrons arriving at x per unit time. but the following interference pattern: 35 . For two slits spaced a distance D apart.
This wave packet is to be zero everywhere except within a region of width ∆ x. That is. Ψ * is the complex 2 * conjugate of Ψ so that Ψ =Ψ Ψ.Evidently. b.0. so the 1 wave function is Ψ ( x) = . x’. 2 2 2 2 2 2 2 2 2 2 Those additional terms in the parentheses are called interference terms. To illustrate. The wave function is nonzero for a region on the xaxis of width ∆ x centered on x = 0. Uncertainty. we find it convenient to use the complex version: Ψ= ∫a 0 k ⋅ e i ( kx −ωt ) dk . where k is the wave number and ak is a Fourier coefficient. The wave function is interpreted as being related to the probability that a measurement will find a particle at a specified location. As is ∞ often the case. ∆x The Fourier transform of Ψ will yield a momentum wave packet. consider a simple rectangular wave packet. 2 will tell 36 . Ψ = Ψ1 + Ψ 2 ≠ Ψ1 + Ψ2 . a(k). It is constructed by a superposition of plane waves ∞ Ψ= ∫a 0 k ⋅ cos( kx −ω ) dk t . rather. * * * Ψ = Ψ1 Ψ1 + Ψ1 Ψ 2 + Ψ1 Ψ* + Ψ* Ψ2 = Ψ1 + Ψ2 + ( Ψ1 Ψ2 + Ψ1 Ψ* ) . The total probability that the particle will be observed somewhere on the xaxis must be 1. a ( k ) us the probability that a particle will be observed to have momentum p = hk.
look at the product ∆x ⋅ ∆p ≈ ∆x ∆x ∆x This relation holds for any pair of conjugate variables. ∆t∆E ≥ [ ∆x∆p = v∆t ∆E = ∆t∆E ] v [The time rate of change of a particle’s kinetic energy: ∆E = v∆ p . p∆x sin 2 2 a( p) = = p π∆x p∆x sin ∆x 2 . p = k. dx = π∆x k ∆x ikx In terms of the momentum. ∆ x. Much theoretical work has gone into determining what sort of mathematical construction will give smooth wave packets with minimum initial uncertainty. since it is a discontinuous function. Now. 2 = . 2 .a(k ) = 1 2π ∆x − ∆x ∫ 2 2 ∆xk sin e 2 2 . it was found that ∆x∆p ≥ .. In fact. 2π p∆x 2 The height of the central peak is much greater than the sidepeaks. For a physically realistic wave packet. e. saying that it is impossible to measure simultaneously both the position (x) and momentum (p) of a particle to arbitrary precision. and the width of the central peak is roughly ∆p ≈ uncertainty relation.g. This is an . a rectangular wave packet is not physical.] 37 .
m =M ⋅ q . Thomson showed that cathode rays are streams of electrons. J. Faraday’s “Law” of Electrolysis demonstrates that i) molecules [NaCl] consist of elemental atoms and ii) subatomic particles have electric charge. chlorine and sodium are deposited on the anode and cathode. The ionized air molecules emit the light seen along the glowing path. The “modern” picture of an atom was assembled in a series of experiments during the 19th and early 20th centuries.D. 38 . Cathode Rays J. Faraday’s “Law” of Electrolysis When an electrical current is passed through molten NaCl. Those electrons escape from one electrode and are accelerated toward the opposite electrode by the applied voltage. e/m a. 1. and q = total charge passed through the NaCl. The ionization is caused by collisions between air molecules and fastmoving electrons. At the time. As we know now. M = molecular weight. the glowing path was mysterious. 2 for O. Atoms The history of the concept of material objects being composed of small particles goes back to the ancient Greeks. Quantitatively. a glowing path of ionized air is formed inside the tube between the electrodes. 96500 Coul ⋅ν where m = mass deposited on the anode or cathode. respectively. and is beyond the scope of this course. when a high voltage is applied to the ends of a partially evacuated glass tube. Charges/particles. etc. Thomson’s experiments established that cathode rays were caused by charged particles. b. ν = valance of the atoms [1 for Na & Cl. subatomic in mass and apparently present in all matter.].
we turn up the Bfield until there is no deflection—the magnetic force on the moving electrons balances the electrostatic force. between two plates. what is the smallest possible charge a particle might have? We suspend a small object. Therefore. We may apply a voltage between the plates and observe the vertical motion of the droplet or bead. Millikan’s experiment The charge to mass ratio of a particle has two properties mixed together. the charge to mass ratio of the electron. and iii) the electrons are released via the photoelectric effect rather than by heating the cathode. 39 . But t = v . so the electron mass is many orders of magnitude smaller than that of an atom. we could obtain e/m. We’d like to get them separately.Pass a stream of electrons through a electric field and a magnetic field oriented at right angles to each other. eE = ev x B whence e θ ⋅ d ⋅V 2 θ ⋅V ≅ = . as shown here: With no Bfield. and do the same with zero applied voltage. knowing vx and measuring θ . To know vx. so v y = mv = mdv . c. vx m x x x tan θ = eVL 2 mdv x e VL = 2 . such as a droplet of oil or a tiny plastic bead. m dv x So. where v y = a y ⋅ t = . For instance. the electron stream hits the screen at the point D. ii) different metals are used for the electrodes. The deflection angle is vy L eEL eVL eE ⋅ t tan θ = . 2 m VL ( Bd ) LdB 2 The electron as a universal constituent of matter is supported by the fact that the same e/m is obtained when i) different gases are in the tube. e/m for the electron is many orders of magnitude smaller than e/m for the Hydrogen nucleus.
many droplets and find that always q = ne. 40 . Without EField With EField At terminal velocity Set EField such that v’ = constant Cv −m = 0 g qE − mg −Cv ′ = 0 C= mg v Substitute for C in the right hand equation. we obtain its mass. so far. qE − mg − mg q g v′ = 1 − m E v v′ = 0 . and W is the weight of the droplet. solve for q/m.Forces on the droplet: D is the air resistance. v Now. that there are both positive and negative charges within an atom. From the volume and density of the droplet. m is the mass of the droplet and q is the excess electric charge on the droplet. m.602x1019 Coulombs. The problem is to arrange them in such a way that they stick together—the atom is stable. how are those blocks arranged? We know. The volume of the droplet can be obtained from Stoke’s “Law” for a sphere falling through a fluid medium. 2. Atomic architecture If atoms are made of smaller building blocks. where n is an integer and e = 1. C is the drag coefficient. such as electrons. We repeat the experiment for many.
φ . We find that r ≈10 −14 meters and that Z is roughly ½ the 2 mα vα 2 atomic weight of the target atom. we find that the positive charge is confined to a very tiny volume. the experiment does not tell us how the electrons in the target atom are arranged within the atom’s structure.) sent a beam of heavy particles (alpha particles) into a thin gold foil. and some even bounce backward. We conclude that the target atoms are several times more massive than the α particle and compact. but not zero. positively charged sphere throughout which are embedded tiny negative particles—the electrons. Rutherford To determine the size of something too small to see. or they orbited the positive nucleus. Just how compact we can estimate by using conservation of energy in a collision. 2 r Solve for that r= kZe ⋅ 2e = f (Z ) 1 . increases. fewer α particles are scattered through that angle. In a direct. However. In other words. As the scattering angle. Thomson Atoms consist of a uniform. 41 . Rutherford (et al. Rutherford proposed that either the electrons were indeed mixed in the positive nucleus. we can bombard that something with tiny projectiles and observe how those projectiles are scattered. φ > π /2. Also still a puzzle was the emission & absorption spectra of atoms. However.a. b. headon collision the α particle reaches closest approach to the target atom when 1 Ze ⋅ 2e 2 mα vα = k . This model gives a stable arrangement of +/.charges. which means that the target gold atoms are not big mushy balls. Just how the positive nucleus could stay together was still a puzzle. it fails to account for the observed emission & absorption spectra. The result was the following: Most α particles are undeviated.
0973732x107m1.1 in the text. so the energy is constant. 4. For Hydrogen: Balmer series: nf = 2 and ni = 3. an accelerated charge emits radiation. . Note the spacing of the lines in each series. the form of Coulomb’s “Law” is exactly the same as the “Law” of Universal Gravitation. The Bohr Model of the Hydrogen Atom Bohr inferred certain properties of the atom from the observed spectra. the emitted radiation should increase in wavelength as the electron continuously loses energy and spirals inward toward the nucleus. for instance. 42 . R = 1. But. . 3. This postulate arises in part from the idea of a standing deBroglie matter wave filling the orbital circumference. according to classical ElectroMagnetism. and ∆ =h . see the Table 4. Their findings are summarized by the following relation: 1 1 = R ⋅ 2 − 2 . During the latter part of the 19th century. In a stable orbit. mvr = n . 5. The problem of atomic spectra Certainly. the electron does not radiate. Energy levels of the Bohr Hatom We use the assumptions mentioned above to see if we can reproduce the observed emission spectra for Hydrogen. iv) The angular momentum of the electron in its orbit is quantized. The attractive force is the Coulomb force. 6. a. That’s how radio signals are generated. These are the experimental results that Bohr set out to explain in his model of the atom.c. An electron in an orbit is certainly accelerated. Assumptions/Postulates i) The electron moves in stable circular orbits about the proton. What is observed? i) Atoms do not emit continuous spectra nor ii) do atoms collapse—they are stable objects. etc. iii) Radiation is emitted when the electron makes a transition from one stable orbit to E f another. it should continuously emit radiation. Further. . and that the series fall in different regions of the EM spectrum. b. an electron could orbit a positively charged nucleus just as planets orbit the Sun. n λ ni f 1 where ni and nf are integers and R is the Rydberg constant. After all. We have two threads: the conservation of energy and the quantization of angular momentum. many individuals measured the spectra of many substances. ii) Only certain orbits are stable.
2 r1 = a o = 2 = 0. The radius of that n = 1 orbit is called the Bohr Radius. is for n = 1. we know that not all values of E are to be permitted. Finally. The first excited state is for n = 2. At the same time. . 3.1 e2 . 4 43 . or ground state energy is E1 = 13. so at this point we invoke the quantization of angular momentum. E 2 = −13 . since for a circular mv 2 − k 2 r e2 mv 2 e2 orbit Newton’s 2nd Law says that k r = . according to the Bohr Model. where m = mass of the electron. 4.4eV . setting mvr = n . v 2 = ke 2 .529 Å. Now. r r r The total energy is E = E= 1 ke 2 ke 2 ke 2 . k = coulomb constant. 2. etc. r. which leads to v 2 = So we have two expressions for v2. 2 n2 n2 2 m2r 2 . − =− 2 r r 2r This is the total mechanical energy of an electron in a circular orbit of radius. . the v and r are not independent. The lowest energy. However. . ao.6eV = −3.6 eV. Substitute this for mv2 in E. mr m2r 2 = ke 2 mr Solve for r = rn rn = n 2 2 mke 2 . n = 1. substitute this rn for r in the expression for E E=− ke 2 =− 2rn 2 2 n2 =− mke 2 Notice the factor of 1 n2 ! These are the allowed energy states of the Hatom. set ‘em equal. e = electric charge of the electron. and the smallest orbit. and n is the principle quantum number. ke 2 mk 2 e 4 1 ⋅ 2 2 n 2 . or mv 2 = k . mke The corresponding lowest.
This 44 . just as it was for fastmoving systems. d. R. so that a single electron orbits a nucleus with charge Ze. So. we would expect to be able to extend quantumbased predictions to macroscopic systems and recover the classical result. 4.c. Hydrogenic atoms We may imagine extreme conditions wherein an atom is almost completely ionized. again just as the classical equations of motion were recovered for speeds small compared to c. λ . Thus. Correspondence Principle Classical. In terms of wavelength. or preModern. only approximate and inaccurate for atomicscale systems. Physics is not incorrect. Then the Bohr Model would say: a ke 2 Z 2 . the 2a o hc Bohr Model of the Hatom can reproduce the observed emission/absorption spectrum. The quantity ke 2 is exactly equal to the experimentally derived Rydberg constant. Hatom spectrum in the Bohr Model Often we chart the allowed energy states on an energy level diagram: The frequency of a photon emitted (or absorbed) in a transition between levels is f = ∆ E ke 2 1 1 = ⋅ − 2 h 2a o h n 2 ni f . 1 λ = f ke 2 1 1 1 1 = ⋅ − 2 =R⋅ 2 − 2 c 2a o hc n 2 ni nf ni f . rn = n 2 o and E n = − 2a o n 2 Z An atom having a single electron orbiting a nucleus is called a hydrogenic atom.
increases.expectation is called a correspondence principle. we might have m ≈1k g and k ≈1 N . To put it another way. so m that ω ≈1 rad . Such a principle serves as a check on quantumbased reasoning and derivations. on the macroscopic scale. where E n = nω and ω = k m .g. in macroscopic systems. the level spacing is too fine to be perceived by the human observer. E. sec the spacing between adjacent energy levels of the Hatom approaches zero as the principle quantum number. Similarly. n. 45 . so the energy appears to be a continuous variable. The spacing between energy levels would be ∆E ≈ ≈1x10 −34 J . In the case of a quantized oscillator (such as a mass vibrating on a spring).
0)e dx . Free Particle A free particle is one subject to no external forces. This equation is known as the Schrödinger Wave Equation for a free particle. Free wave packet A wave packet for a free particle is constructed of many plane waves: +∞ Ψ x. we want a scheme of producing equations of motion. 2. 46 . That is. etc. Wave equation This Ψ . charge. y =e p2 y = A sin px − 2m Which form is used in a given case is a matter of convenience. energy. Schrödinger Wave Equation—One Dimensional 1. Interpretation of the Wave Function. t ) = ( −∞ ∫ a ( k )e i ( kx − t ) ω dk = + ∞ 1 2π +∞ −∞ ∫ a ( p )e i ( kx − t ) ω 2 i px − p t 2m dp . a. Quantum Mechanics & Atomic Structure (abbreviated) We now seek a full treatment of particle dynamics in terms of matterwaves. Ψ a. A plane wave with this E and p would be written: 2m . The transform gives the coefficients: a (k ) = −∞ ∫ Ψ( x. E = number.III. 2 2m ∂x ∂t which can be verified by substitution. b. momentum. EinsteindeBroglie relation i p2 px − t E = ω and p =k . where p is the momentum. m is the mass. Claim The wave function contains all the information that can be known about a particle—its mass. a superposition of plane waves. A. An alternative form is p p2 is the kinetic energy and k = is the wave 2m p2 t + B cos px − 2m t. satisfies the following differential equation: 2 − ∂2 ∂ Ψ = i Ψ. c.
b. Proposed interpretation The probability that the particle will be observed to be at a location between x and x+dx at time t * x ( x is given by P ( x, t )d =Ψx, t ) 2 d , where Ψ2 =Ψ Ψ and P(x,t) is the probability density. To be realistic, Ψ must be continuous and single valued and must be normalized, since
+ ∞ − ∞
∫Ψ
2
dx =1 .
That is, the particle must be somewhere on the xaxis. This proposed
interpretation is to be validated by experiment. c. Solving for the motion The problem, then, is to find Ψ (x,t), given Ψ (x,0), rather than x(t) given x(0), as in Newtonian 2 mechanics. We shall have to make the connection between Ψ and the physical motion of the particle explicit subsequently. That is, later. 3. Particle Experiencing a Conservative Force
We draw an analogy with a wave propagating in a dissipative medium. a. Schrödinger equation
−
2 ∂2 Ψ ∂Ψ +U ( x )Ψ = i , 2 2m ∂x ∂t
where U(x) is the potential energy function for the external conservative force. The solution of this equation may be easy or difficult, depending on the form of the U(x). Even so, we’re assuming the potential energy function is constant in time. b. Time independent Schrödinger equation If the U is not a function of time, then the differential equation is separable, in the usual way. We assume that Ψ( x, t ) =ψ( x ) ⋅φ(t ) . Then
−
2 ∂ 2ψ i ∂φ +U ( x ) = =E, 2mψ ∂x 2 φ ∂t
where E is the constant total energy of the particle. The space (x) equation to be solved is 2 ∂ 2ψ − +U ( x)ψ = Eψ . 2 To go farther, we need to consider specific potential energy functions.
2m ∂x
47
B. 1. a.
OneDimensional Potentials Infinite Well or OneDimensional Box U(x)
∞ x ≤0 x ≥L U (x ) = ∞ 0 0 < x < L
b.
Conditions on ψ
0 ψ = 0 ( x) ψ
x ≤0 x ≥L 0 <x <L
c. Solution We have 3 regions in which the Schrödinger equation must be solved. Two regions are taken care of already in this case, as ψ = 0 outside the potential well. Inside the well, U = 0, so the particle is free. d 2ψ 2mE = − 2 ψ = −k 2ψ 2
dx
This is the equation for a plane wave, so for 0 < x < L,
ψ( x) = A sin( kx ) + B cos( kx ) .
To evaluate the coefficients, A & B, we apply the boundary conditions. We require that ψ (0) = 0 and ψ (L) = 0. since B = 0. If both A & B are zero, we have the trivial solution, ψ = 0 . d. Energy levels Because sin(kL) = 0, there is a restriction on the energy of the particle in the well. Evidently, kL = nπ , where n = 1, 2, 3, 4, 5, . . . Substitute for k in the total energy
E=
2 2 k 2 n 2π 2 π 2 2 = = n2 , n = 1, 2, 3, 4, 5, … 2m 2mL2 2mL2
0 = A sin( 0) + B cos( 0) ⇒B = 0 0 = A sin( kL ) + B cos( kL ) ⇒sin( kL ) = 0 ,
Note: i) the quantized energy levels arise from the boundary conditions and ii) the lowest possible energy is E1 =
π 2 2
2mL 2 ≠ 0 . This lowest possible energy is called the zeropoint energy,
even though it isn’t zero. e. Normalization
nπx . We evaluate A by L The wave functions corresponding to the energy levels are ψ n = A sin
nπx dx = ∫ A 2 sin 2 dx = 1 L Use the identity 2 sin 2 θ = 1 − cos 2θ .
setting ∫ψ
2
d = . x 1
∫ψ
2
48
∫
0
L
A2 2
A2 n 2πx 1 − cos ( L − 0) = 1 ; solve for A = dx = 2 L
2 nπx sin . [See Fig. 5.7 and 5.9 in the text.] L L
2 . L
Because the wave function is zero outside the well, we integrate from 0 to L rather than ±∞ . Finally, we have ψ n = 2.
Expectation Values
a. Weighted averages When averaging a list of values, we say
< A >=
∑p A
i i =1 N
N
i
∑
i =1
, where pi is the number of times the value Ai appears in the list having N
pi
different values. b. Probability & expectation 2 Ψ is the probability density, giving the odds that the particle will be observed to be in Now, the state described by Ψ (x,t). Suppose we make many observations of the position of the particle. Then the average of our observations would be 2 * <x > ∫ xψ d =∫x ψ d . = ψ x x This is called the expectation value of x. The standard deviation of many observations of x is
x =∆
∆x =
(∑ xi− x>< )
N
N
.
2
∑x
∫x
2
2 i
−2< x >
∑x
i
+ m < x >2
∆ x = < x2 > − < x > 2
where we could calculate c.
<x 2 > =
,
ψ d x
2
particle momentum
49
We define the expectation value of the particle momentum as < p > =m d< x> . ∆ p = < p 2 > − < p > 2 . 50 . this expression reduces to p = mv. For dt macroscopic objects. Also.
C. polar coordinates The Coulomb force is spherically symmetric. a. b. 2. U ( r ) =U ( r ) and we can separate the variables by assuming that ψ = R (r )Θ θ)Φ ϕ) . where ∇2 = 2 + 2 + 2 ∇ Ψ +U ( r ) Ψ = i ∂x ∂y ∂x 2m ∂t −iωt The solutions have the form Ψ( r . ( ( − − 2 ∂2 2 ∂ 1 ∂2 ∂ ∂ 2 + + 2 2 + cot θ + csc 2 θ ψ ( r ) + (U ( r ) − E )ψ ( r ) = 0 2 2 2m ∂r ∂θ ∂ϕ r r r ∂θ 2mr 2 2 2 ∂2 ∂2 ∂ ∂ ∂2 r ψ + + 2r + cot θ + csc 2 θ ∂r 2 ∂θ 2 ∂r ∂θ ∂ϕ 2 Multiply through by − Collect the terms depending on r and divide through by ψ . so it’s convenient to use spherical polar coordinates. 1. Angular momentum—the angular parts 51 . Central Forces. t ) =ψ( r )e . 2mr 2 ψ − (U (r ) − E )ψ = 0 2 r 2 ∂2 2r ∂ 2mr 2 1 ∂2 cot θ ∂ csc 2 θ ∂ 2 R+ R− (U (r ) − E ) + Θ+ Θ+ Φ=0 2 2 2 R ∂r R ∂r Θ ∂θ Θ ∂θ Φ ∂ϕ 2 We’ll have to solve this thing one piece at a time. Wave equation in polar coordinates 2 ∂2 2 ∂ 1 ∂2 ∂ ∂ 2 + csc 2 θ ψ ( r ) + U ( r )ψ ( r ) = Eψ ( r ) 2 + + 2 2 + cot θ 2 2m ∂r ∂θ ∂ϕ r ∂r r ∂θ For central potentials. ThreeDimensional Potentials Threedimensional Schrödinger Equation − 2 ∂2 ∂2 ∂2 2 ∂Ψ .
We identify m with the angular momentum about the z axis. rearrange Θ ∂θ Θ ∂θ sin θ d dθ d Θ + C sin 2 θ − m 2 Θ = 0 .1. Define: ≡ orbital quantum number and m ≡ magnetic quantum number.1 ∂2 cot θ ∂ csc 2 θ ∂ 2 Θ+ Θ+ Φ = −C Θ ∂θ 2 Θ ∂θ Φ ∂ϕ 2 C is the separation constant.and y axes.2.. another separation constant. “well known” differential equation—the Associated Legendre Equation.. ± 1 2 3 The other constant is identified with the magnitude of the total angular momentum L2 = ( +1) 2 . sin θ dθ ( ) This is a standard.. = 0.± . which equation has familiar solutions Φ ∂ϕ 2 Substitute this into the θ equation Φ = e ±im ϕ . ...± .3.− +1..± . −1. 52 . m = 0. which is quantized: ˆ L z = m .. The solutions are bounded and differentiable (the physical requirements) if C = ( +1) and m = − .. Θ ∂θ 2 Θ ∂θ Φ ∂ϕ 2 Set − 1 ∂2 Φ = m 2 .. Multiply by sin 2 θ sin 2 θ ∂ 2 cos θ sin θ ∂ 1 ∂2 Θ+ Θ+ Φ = −C sin 2 θ Θ ∂θ 2 Θ ∂θ Φ ∂ϕ 2 Separate again sin 2 θ ∂ 2 cos θ sin θ ∂ 1 ∂2 Θ+ Θ + C sin 2 θ = − Φ = m2. 2 ˆ ˆ Note: C sin 2 θ − m ⇒ combination of angular momentum about the x . sin 2 θ ∂ 2 cos θ sin θ ∂ Θ+ Θ + C sin 2 θ = m 2 ...
but so is the Lz. 2 R + 2m dr r dr 2mr 2 The allowed energy levels are obtained from the boundary conditions applied to R(r). this will give the principle quantum number. − 2 d 2 L2 2 d R + R + U ( r ) R = ER . U (r ) = − e.3 in the text] d. Radial equation The radial part of the wave equation remains. 2 L2 = ( +1) = 2 2 . The details depend on the exact form of U(r). m L cos θ = z = The condition L ( +1) m = − .+ . for = 1 .7 in the text shows the case of =2. 2 2 Fig. n. 1 1 gives the allowed projections on the z1 1 . 53 . For instance. =1 . Spherical harmonics The “well known” solutions to the Associate Legendre Equation are the Spherical Harmonics: Θ(θ )Φ(ϕ) = Ym (θ . cos θ = − axis. ke 2 . and .0 so L z = − . 7. In the case of the Hydrogen atom.0.c. r Angular momentum vectors Lz is the projection of L on the zaxis. [see Table 8. Not only is the L quantized. ϕ) 1 Y00 = 2 π 1 3 Y10 = cos θ 2 π 1 3 Y1±1 = sin θ ⋅ e ±iϕ 2 2π etc.+ .0. The vector L precesses around the zaxis. For .
while a lower case d stands for an = 2 subshell. This is what determines the allowed energy levels. Given U(r). En. 2 2 n 2 En = − ke 2 1 . ϕ )e −iωt . These states are said to form a shell. See Table 7. . 4. 2. 54 . 3. the letter K stands for the n = 1 shell. R(r)—degeneracy. t ) = R (r )Y (θ . . the allowed values of m for a specified form a subshell. ϕ. 2a o n 2 Commonly. 1.4 in the textbook. . The boundary conditions j will require that R(0) = 0 and that R → 0 as r → ∞ . Radial Equation − 2 d 2 L2 ke 2 2 d R + R + R− R = ER 2 2m dr 2 r r dr 2mr The whole equation is multiplied by r. n = 1. En = − mk 2 e 4 1 . . m combinations may apply to the same energy state. we write En in terms of the Bohr radius It follows that the allowed orbital (angular momentum) states are =0.D. .. .θ . 2. Notice that many . 2. We still use the naming scheme created by the preModern spectroscopists who measured atomic spectra in the 19th century. The latter condition restricts the series to be a finite polynomial with the highest j = n > . The Hydrogen Atom U (r ) = − ke 2 r m So far we have Ψ(r . the allowed values of and m label states having the same energy. we have to find R(r). n1. (rR ) + − 2mr 2 2m dr 2 r j A standard method of solution is to try a power series: R = ∑a j r . Then the second derivative term can be collapsed to − L2 2 d 2 ke 2 ( rR ) = E ( rR ) . 3. Spectroscopic Notation For a specified n. 1. As shown in the following table.
0 2 = e .m = Rn..e. The probability density is ψ 1.0. 1s 3 πa o ao 2 2 Note that P( r ) =r R (r ) and that ∞ 0 P ( r ) d =ψ 4π 2 d r r r 2 . P(r) such that − 4 For ψ100 . the distance of the electron from the atomic nucleus. 3. Ground state ψ1. (r )Ym (θ . <r > = ∞ 0 ∫ rP (r )dr 2r ao < r >1s = ∫ r 0 ∞ 4 3 ao r e 2 − dr = ∫ 4 3 ao r e 3 − 2r ao dr 55 .0. . In fact. Further. 3 πao − 2r ao which is also spherically symmetric. Probability Densities ψ n. m ) arise from physical restrictions placed on the mathematical solutions to the Schrödinger equation. We define the Radial Probability Distribution. all states with = 0 are spherically symmetric. ϕ ) a. 2r − ao 2r ∫ P(r )dr =1 . since = 0 i. there is one quantum number for each degree of freedom. We can calculate the expectation value of r.0Y00 1 1 = π ao 2 − ao e 3 r This function is spherically symmetric.0 = R1. P(r ) = P (r ) = e 4πr 2 = 3 r 2 e ao .n(shells) 1 2 3 4 5 6 symbol K L M N O P (subshells) 0 1 2 3 4 5 symbol s p d f g h We see that the quantum numbers ( n. it’s an sstate..
in circulating about the proton. thus: e Jouls eV = 9. the 2p states are ψ2. and ψ2. Magnetic moments Viewed in preModern terms. . we define the geomagnetic ratio to be where q is the particle charge and m is the particle mass. then m = 1. there are 4 states with the same energy.0 . b. The orbital quantum number.1. having a magnitude of µ = jA . −1 . For any charged particle. the orbiting electron creates a magnetic dipole field. ψ2. E2.5ao 3 4 16 ao 2 a o Notice: While r = ao is the most probable radius. is quantized: µ z = −µ B ⋅ m . the expectation value of the radius is <r> = 1. 2 2 2 ψ200 ψ211 or ψ1 − 2 1 ψ210 2 4. like Lz. 2m Notice the chargetomass ratio: e/me. According to the spectroscopic notation.1 . 56 . The T magnetic moment vector becomes µ = µB = − e LT − eL = .5ao.0 . Normal Zeeman Effect a. may be 0 or 1. First excited state In the first excited state.788 x10 −9 .274 x10 −24 = 5.0.< r >1s = 4 3! 24 = a o = 1. then j = −e . 2m e Tesla Gauss q . On T the other hand. the 2s state is ψ2. the magnitude of the orbital angular 2 me A momentum. The dipole moment is µ. n = 2.1. is L = . where j is the timeaveraged electrical current and A is the area of the closed orbit. that is. Therefore. according to Kepler. The quantity that appears in the magnetic moment is ½ the chargetomass ratio. We say that the degeneracy is 4fold. If T is the orbital period. averaged over a large number of observations of r. T 2me 2me It’s convenient to define the quantity called the Bohr Magneton.1. If =1 . 0. or +1. The zcomponent of µ.
Larmor precession In an externally applied magnetic field.b. c. ±l . In the presence of a strong magnetic field. ±3 . all the n = 2 states have the same energy. then ˆ E = E 2 + ωL m is the energy with the Bfield. is characterized by the splitting of spectral lines into sets of several uniformly spaced lines in the presence of a strong magnetic field. Normal Zeeman effect With no external Bfield. . the more m values there are. dL . We call this lifting the degeneracy. E2. a magnetic dipole will experience a torque. dt dL L sin θ dL = L sin θ ϕ = τ dt = d e LB sin θ dt 2 me . The Normal Zeeman Effect. then. ± 2 . the formerly degenerate energy levels are separated by ± mωL . ωL = = e LB sin θ eB = 2me L sin θ 2 me This precession rate is called the Larmor Frequency. ±1 . . where we 2me 2me have assumed that B = Bz . The higher the value of n. ∆E = −µ ⋅ B = e eB L⋅B = L z . The since the dL ⊥ µ and B . Thus. .. 57 . τ = µ×B = dt µ vector precesses around an axis aligned along the B . Since m = 0 . the interaction of the orbital magnetic dipole with the externally applied magnetic field leads to a change in the energy. if E2 is the state energy without the Bfield.
For electrons. visualized as spinning. Stern –Gerlach experiment Atoms passing through a nonuniform magnetic field: any net magnetic dipole possessed by the atoms will cause them to be deflected. Interpretation: i) the effect is not due to the orbital magnetic moment. s. Fine Structure a. the gfactor is found experimentally to be g = 2 . else there would be either 2 +1 or zero spots on the screen and ii) the deflections are due to a magnetic moment that has only two possible values. Since Stern & Gerlach obtained 2 s + 1 = 2 . This value indicates that the electric charge is not uniformly distributed in a tiny solid rotating sphere as our classical visualization depicts it. c. In analogy to orbital angular momentum. d. there are often nonuniform splittings of spectral lines. The observed result is that the atomic beam is divided into two beams with equal but opposite deflections. The quantity g is 2me called the gfactor.5. Electron spin We propose that a magnetic moment is produced by the electron itself. These are not accounted for by the orbital µ. we infer that for the 1 1 and that m s = ± . we define a spin quantum number. These are called the anomalous Zeeman splittings. This S2 electron s = is constant. the total magnetic moment of an electron in an orbit about a proton is µ = µ + µ s = −e L + gS . which is a kind of a fudge factor. such that the number of possible angular momentum zcomponents is 2 s +1 . while S 2 = s ( s +1) 2 . so this thing called spin is an intrinsic property of the electron as much as are its mass and electric charge. b. 2 me ( ) 58 . Anomalous Zeeman effect In addition to the uniformly split lines due to the normal Zeeman effect. The zcomponent of the spin 2 2 angular momentum is S z = ms . Total magnetic moment of an electron With these two contributions. The spin magnetic moment is µ s = g e S .
What was once a single electron level becomes two. With the electron in the moment B . j. so j takes on the values ± e. . s =± 2 1 5 1 3 then j = 2 + = and j = 2 + − 1 = 2 2 2 2 59 . µs : τ = µs × B The potential energy contribution is − eg µ e2 g S . we introduce a new quantum number. B = − 2m e a o moment..g.6. J The total angular momentum of the isolated Hydrogen atom is conserved: J = L + S . b. j+1. By analogy (again). . where B = = − o and B = − 2me R 2R 2R 3 µo e L . Call the Bfield due to this µo e µ o (−e)vR 2 µ ev L . Total angular momentum. This B exerts a torque on the spin magnetic first Bohr orbit. based on the quantum restrictions on L and on S . S has two U = − µ s ⋅ B = − o L ⋅ S . SpinOrbit Interaction a. so U may raise or lower the energy level. . Potential energy of two magnetic dipoles The orbital angular momentum gives rise to a magnetic moment. 1 for atomic electrons. j1. This is called fine structure doubling. R = ao. since µ s = 2me 2 me a o possible orientations. What is the range of j? J is the sum of L and S . such that J 2 = j ( j +1) 2 and J z = m j . with mj = j. 2 1 =2. Let us examine the possible values J can have.
± . [ 2 ⋅ +1 = 2 ] 2 2 2 3 3 1 3 j = ⇒ = 1 ⇒ m j = ± .g. etc. f. 2 2 2 9 9 7 5 3 1 9 j = ⇒ = 4 ⇒ m j = ± . the Sodium doublet c. P. D. s =± The number of mj values is 2j + 1.± . etc.± . j = ± . so there are 2 ± +1 values of mj—the projection of J on the zaxis. e. j= fine structure. 1 2 1 9 1 7 then j = 4 + = and j = 4 + − 1 = 2 2 2 2 =4.g.e. for the energy states we use the capital letters S. d. [ 2 ⋅ + 1 = 4 ] 2 2 2 2 3 3 1 j = ⇒ = 2 ⇒ m j = ± . Spectroscopic notation number for n capital letter for orbital angular momentum subscript for total angular momentum n = 2 = 0 ⇒ 2S 1 2 j = 1 2 n = 3 = 2 ⇒ 3D 5 2 j = 5 2 e. p.± . 60 . In terms of .g.± . [ 2 ⋅ + 1 = 10 ] 2 2 2 2 2 2 2 Each mj level has slightly different energy since the angle between µs and B is different 1 2 1 2 e. 1 1 1 ⇒ = 0 ⇒ m j = ± .g. The usages of the 2 schemes of spectroscopic notation goes as follows: for orbital subshells we use the lower case letters s.± .
That is. 3s. With electron spin. etc. Shells & subshells We envision the atomic energy levels to be labeled by quantum numbers n and 1s. Multielectron Atoms Two effects are important: i) screening of the nucleus and ii) the exclusion principle. within a shell. or orbitals. These are called shells. no more than 2 electrons can occupy an atomic subshell. spin up and down. but in different subshells. so each shell may be occupied by up to 2( 2 +1) electrons. 2p. This has implications for the electronic structure of multielectron atoms and the periodic table of elements. The shells are divided into 2 +1 subshells. 2. each electron interacts not only with the atomic nucleus. Exclusion principle It turns out that no two electrons within an atom can be in exactly the same quantum state. According to the exclusion principle. the outermost subshell is partially filled. with m s = ± . since their probability densities are spherically symmetric around the nucleus. These are the valance electrons. 3. 1. each subshell has two levels. However. 61 . Hund’s Rule Each orbital (subshell) holds two electrons. the subshells are filled in order of increasing energy. according to m . the twoelectron Helium atom: The net effect is that electrons farther from the nucleus “see” a nuclear charge of something less than Ze. Nuclear Screening In a multielectron atom. no two electrons in an atom can have exactly the same set of values for their quantum numbers. 4f. b. one electron may occupy each level. In the atomic ground states. The energy states are not simply the same ones found for the Hatom. This means in practice that it is practically impossible to solve for the multielectron energy states exactly— they have to be approximated to some degree. but also with every other electron in the atom. Commonly. Electronic Configurations of the Elements 1 2 a. lower energy is usually obtained if the spins are aligned. Namely. This is a property of a class of subatomic particles called fermions. For instance.E.
atom H He Li Na config 1s1 1s2 1s22s1 1s22s22p63s1 1s ↑ ↑ ↑ ↑ 2s ↑ ↑ 2p 3s ↑ ↑ ↑ ↑ As n increases.. So there are quirks in the order in which shells are filled up. 62 . K is not [Ne] 3s23p63d1.2 for the ground states of the elements. e. 3d54s1 for Cr.g. where “4s~3d” means these states have nearly the same energy. look at V. the spacing between levels decreases. is placed in each orbital. . and Mn.g. Oxygen & Fluorine 2p shell Oxygen Fluorin e ↑ ↑ ↑ ↑ ↑ ↑ c. and the number of electrons in each orbital. See Table 8.e. Notation The electronic configuration is written out by listing the occupied orbitals. the energy levels are ordered thusly: 1s<2s<2p<3s<3p<4s~3d<4p<5s<4d<5p<6s<4f~5d<6p<7s<6d~5f. so the 4s level fills before the 3d level is occupied. .g. spins aligned. with opposite spin. for Carbon 2p shell this ↑ ↑ rather than ↑ m = −1 0 +1 This is Hund’s Rule: a shell is filled first with one electron in each orbital.g. The 4s level is of lower energy than 3d. Then the second electron. Evidently. see the elements 18 – 30. . worse. but [Ne] 3s23p64s1. 3d54s2 for Mn. The outer most shells are 3d34s2 for V. e. Cr. e.g. e.