Quantum Mechanics Formulas: by R.L.

Griffith@ UCB
Physical Constants
Name
Number
Number e
Eulers constant
Elementary charge
Gravitational constant
Fine-structure constant
Speed of light in vacuum
Permittivity of the vacuum
Permeability of the vacuum
(40 )1

Symbol
Value
Unit

3.14159265358979323846
e
2.71828182845904523536
 n

P
= lim
1/k ln(n) = 0.5772156649
n

k=1

e
G,
= e2 /2hc0
c
0
0

Plancks constant
Diracs constant
Bohr magneton
Bohr radius
Rydbergs constant
Electron Compton wavelength
Proton Compton wavelength
Reduced mass of the H-atom

h
~ = h/2
B = e~/2me
a0
Ry
Ce = h/c
Cp = h/mp c
H

Stefan-Boltzmanns constant
Wiens constant
Molar gasconstant
Avogadros constant
Boltzmanns constant

kW
R
NA
k = R/NA

Electron mass
Proton mass
Neutron mass
Elementary mass unit
Nuclear magneton

me
mp
mn
mu =
N

Diameter of the Sun

Mass of the Sun
Rotational period of the Sun
Radius of Earth
Mass of Earth
Rotational period of Earth
Earth orbital period
Astronomical unit
Light year
Parsec
Hubble constant

D
M
T
RA
MA
TA
Tropical year
AU
lj
pc
H

1.60217733 1019
6.67259 1011
1/137
2.99792458 108
8.854187 1012
4 107
8.9876 109

6.6260755 1034
1.0545727 1034
9.2741 1024
0.52918
13.595
2.2463 1012
1.3214 1015
9.1045755 1031
5.67032 108
2.8978 103
8.31441
6.0221367 1023
1.380658 1023

1
12
12 m( 6 C)

9.1093897 1031
1.6726231 1027
1.674954 1027
1.6605656 1027
5.0508 1027

1392 106
1.989 1030
25.38
6.378 106
5.976 1024
23.96
365.24219879
1.4959787066 1011
9.4605 1015
3.0857 1016
(75 25)

C
m3 kg1 s2

m/s (def)
F/m
H/m
Nm2 C2
Js
Js
Am2

A
eV
m
m
kg
Wm2 K4
mK
Jmol1 K1
mol1
J/K
kg
kg
kg
kg
J/T
m
kg
days
m
kg
hours
days
m
m
m
kms1 Mpc1

Chapter 2: Stationary States

Chapter 1: The wave Function

seperation of variables

Schrodinger Equation
i~

~2 2
=
+V
t
2m x2

(1)

(x, t) = (x)(t) = (x)eiEt/~

(12)

Probability
b

Pab =

|(x, t)|2 dx

d
iE
=
dt
~

(13)

(t) = eiEt/~

(14)

(x, t) = (x)eiEt/~

(15)

(2)

For Normalization

1=

|(x, t)|2 dx, where |(x, t)|2 =

Time Independent Schrodinger equation

(3)
once is normalized it stays normalized for
all time

~2 d2
+ V = E
2m dx2

(16)

Hamiltonian
d
dt

|(x, t)|2 dx = 0

(4)

Operators for momentum and position in general form

Z

xdx


Z
~

dx
hpi =
i x


Z
~

hQ(x, p)i = Q x,
dx
i x
hxi =

p2
+ V (x)
2m

H(x, p) =

substitute p = (~/i)(/x) and the corresponding Hamiltonian operator is

(5)

2 2
= ~ d + V (x) = E
H
2m dx2

(18)

hHi = Hdx
=E

(19)

(6)

You can always write the general solution of

the Schrodinger equation as a linear combination
of seperable solutions

(7)

Expectation value of kinetic energy

2

hT i =

~
2m

(8)

(x, t) =
2~
h
=

cn n (x)

(20)

n=1

de Broglie formula
p=

(x, 0) =

dx
x2

(17)

cn n (x)eiEn t/~ =

n=1

(9)

cn n (x, t)

n=1

(21)

The Infinite Square Well

uncertainty principle
V (x) =
~
x p
2

(10)




x
x

0, if 0xa
, otherwise

(22)

plugging this into the TISE and we get

probability current
i~
J(x, t)
2m

(11)

d2
= k 2
dx2

(23)

2mE
k
~

(24)

The harmonic Oscillator

(x) = A sin kx
n
kn =
a
n2 2 ~2
En =
2ma2

(25)
1 2
kx
2
r
k

m
1
V (x) = m 2 x2
2

(27)

after normalization, the general TISE solutions for the infinite square well is
n (x) =

 n 
2
sin
x
a
a

m (x) n (x)dx = 0

(28)

m (x) n (x)dx = mn
mn =

0, if m6=n
1, if m=n

1
(ip + mx)
(42)
a+
2~m
1
a
(ip + mx)
(43)
2~m
1
[p2 + (mx)2 imw(xp px)]
a a+ =
2m~
(44)

(29)

commutator

(30)
(31)

we say that s are orthonormal

4. They are complete, in the sense that any
other function, f (x), can be expressed as a linear
combination of them:

n (x) f (x)dx

(34)

Pn = |cn |2

(35)

|cn |2 = 1

(36)

n=1

hHi =

n=1

|cn |2 En

(45)

[x, p]f (x) = i~f (x)

(46)

[x, p] = i~

(47)

1
1
H+
~ 
2

H = ~ a a+

(48)
1
2

1
1
H
~
2
[a , a+ ] = 1


1
H = ~ a+ a +
2
a+ a =

(33)

r Z a
 n 
2
x (x, 0)dx
sin
=
a 0
a

[A, B] AB BA

a a+ =

 n 
2X
f (x) =
cn n (x) =
x
cn sin
a n=1
a
n=1
(32)
the cn s can fe found using Fouriers trick

cn =

(40)

1 2
[p + (mx)2 ] = E
(41)
2m
we can use raising and lowering operators to
solve this problem

Kronecker delta
Z

(39)

rewriting equation 18 in a more suggestive

form

as a collection, the functions n (x) have some

interesting properties
1. They are alternately even and odd, with
respect to the center of the well.
2. As you go up in energy, each succesive
state has one more node (zero crossing)
3. They are mutually orthogonal, in the
sense that
Z

(38)

V (x) =

(26)

(49)
(50)
(51)
(52)

In terms of a , then the Schrodinger equation

of the harmonic oscillator takes the form

(37)



1
~ a a
= E
2

(53)

H(a+ ) = (E + ~)(a+ )
H(a ) = (E ~)(a )

(54)
(55)

there must be a lowest state and this occurs

when
a 0 = 0

p = ~k
r

(56)

vquantum =

this means

(70)
E
2m

(71)

vclassical = 2vquantum



1
d

+ mx 0 = 0
~
dx
2~m

(57)
1
(x, t) =
2

the genral solution for the ground state of the

harmonic oscillator is
0 (x) =

 m 
~

2
m
2~ x

(59)

x=

(61)

p=i

1
(k) =
2

(65)

(75)
(76)

(x, 0)eikx dx

(77)

E<0

bound state
E>0 scattering state

(66)

(x)

V (x) = 0 everywhere
~k

(x, t) = Aeik(x 2m t + Beik(x+ 2m t)

~k2

(74)

The Delta-Function Potential

The Free particle

k (x, t) = Aei(kx 2m t

(k)eikx dk

so the solution to the generic quantum problem, for the free particle is equation 74, with

(64)

~m
(a+ a )
2

~k

Z
1
f (x) =
F (k)eikx dk
2
Z
1
F (k) =
f (x)eikx dx
2

a n = nn1 (63)

~
(a+ + a )
2m

this is a classic problem in Fourier analysis;

the answer is provided by Plancherels theorem

(60)

1
n = (a+ )n 0
n!

(73)

to determine (k) we can use the TISE which

a a+ n = (n + 1)n (62)

a+ n = n + 1n+1 ,

~k2

(k)ei(kx 2m t) dk

1
(x, 0) =
2

1
~
2


1
En = n +
~
2
n = An (a+ )n 0 (x)

a+ a n = nn ,

is

(58)

E0 =

(72)

0, if x6=0
, if x=0

, with

f (x)(xa)dx = f (a)

(78)

(x)dx = 1
(79)

(xa)dx = f (a)

(80)
thats the most important property of the
delta function: Under the integral sign it serves
to pick out the value of f (x) at the point a.
Lets consider a potential of the form

(67)

(68)

V (x) = (x)

n
2mE
travelingtotheright
, with k>0
k
k<0 travelingtotheleft
~
(69)

(81)

plugging this into equation 18 in the region

x < 0, V (x) = 0 so
4

where

2mE
d2
= 2 = k2
2
dx
~

(82)

2mE
k
~

(83)

2mE
k
(92)
~
is real and positive. The general solution is
for x < 0

where

(x) = Aeikx + Beikx

for bound states E < 0 the general solution is

when x < 0
(x) = Aekx + Bekx

and this time we cannot rule out either term,

since neither blows up. and similarly for x > 0

(84)

(x) = F eikx + Geikx

the first term blows up as x so we

must choose A=0
(x) = Bekx

F +G=A+B

for bound states E < 0 the general solution is

when x > 0

the second term blows up as x

must choose G=0

Bekx ,
(x0)
Bekx , (x0)

(87)

ik(F G A + B) =

d
dx

2m
(0)
~2

(x) =

m m|x|~2
m2
e
; E= 2
~
2~

m
~2 k
(98)
having imposed both boundary condition we
are left with two equations and four unknowns.
it follows A is the amplitude of a wave coming
from the right, B is the amplitude of the wave
returning to the left, F is the amplitude of the
wave traveling of to the right, and G is the amplitude of the wave coming in from the right.

(88)

(89)
G = 0, for scattering from the left
A = 0, for scattering from the right

(99)
(100)

for scattering from the left, A is the amplitude

of the incident wave, B is the amplitude of the
reflected wave, and F is the amplitude of the
transmitted wave solving equations 95 and 98
for B and F , we find

(90)

What about scattering states, with E > 0?For

x < 0 the Schrodinger equation read
2mE
d2
= 2 = k 2
2
dx
~

(97)

F G = A(1+2i)B(12i), where

Evidently the delat-function well, regardless

of its strength , has exactly one bound state

2m
(A + B)
~2

or more compactly

the second boundary condition gives

d/dx=ik(F eikx +Geikx ), for(x>0), so d/dx|+ =ik(F G)

d/dx=ik(Aeikx +Beikx ), for(x<0), so d/dx| =ik(AB)

(96)
and hence (d/dx) = ik(F G A + B),
meanwhile (0) = (A+B), so the second boundery condition says

so we

It remains only to stitch these two functions

together, using the appropriate boundery conditions at x = 0, the standard boundary conditions
for
1. is always continuous 2. d/dx is continuous except at points where the potential is
infinite
in this case the first boundary condition tells
us that F = B, so
(x) =

(95)

the derivatives are

(86)

(x) = F ekx

(94)

for boundary condition number 1 this implies

(85)

(x) = F ekx + Gekx

(93)

B=

(91)
5

i
1
A, F =
A
1 i
1 i

(101)

The reflection coefficient is

R

|B|2
2
=
|A|2
1 + 2

and the general solution is

(102)

(x) = C sin(lx) + D cos(lx),

for a < x < a

(114)
when x > a the genral solution is

and the transmission coefficient is

T

1
|F |2
=
|A|2
1 + 2

(103)

(x) = F ekx + Gekx

the first term blows up as x so we

must choose G=0

and the sum should be one

R+T =1

(104)
(x) = F ekx ,

R and T are functions of and hence functions of E

1
1 + (2~2 E/m2 )
1
T =
1 + (m2 /2~2 E)

R=

V0 , for axa
0,
for |x|>a

(105)
(106)

(107)

F eka = D cos(la)

This potential admits both bound states and

scattering states. we will look at the bound
states first. in the region x < a the potential
is zero, so the Schrodinger equation reads
2mE
d2
= 2 = k2
dx2
~

for x > a

kF eka = lD sin(la)

(118)

deviding equation 118 by 117 , we find that

(108)

k = l tan(la)
2mE
~

(117)

and the continuity of d/dx, says

where

(116)

The next step is to impose boundary conditions: and d/dx continuous at a and a.
but we can save a little time by noting that this
potential is an even function, so we can assume
with no loss of generality that the solutions are
either even or odd. since (x) = (x).
for even solutions use D cos(lx) and for odd
solutions use C sin(lx). I will show the even solutions
The continuity of (x), at x = a, says

The Finite Square Well

V (x) =

(115)

(119)

This is a formula for the allowed energies,

since k and l are both functions of E. To solve
for E, we first adopt a nicer notation: Let

(109)

the general solution as before is

(x) = Aekx + Bekx

z la,

(110)

the first term blows up as x so we

must choose A=0
(k 2 + l2 ) =
(x) = Bekx ,

for x < a

(111)

and z0

ap
2mV0
~

2mV0
, so ka =
~2

(120)

q
z02 z 2 (121)

and now equation 119 read

in the region a < x < a,V (x) = V0 , and

the Schrodinger equation reads

tan(z) =

p
(z0 /z)2 1

(122)

This is a trancendental equation and can olny

be solved numerically or graphically. Two limiting cases are of special interest.
1. Wide, deep well. if z0 is very large,
the intersections occur just slightly below zn =
n/2, with n odd it follows that

~2 d2
d2
V0 = E, or
= l2
2
2m dx
dx2
(112)
where
p
2m(E + V0 )
l
(113)
~

n2 2 ~2
En + V0
=
2m(2a)2

continuity of d/dx at +a gives

(123)
l[C cos(la) D sin(la)] = iF eika

2. Shallow, narrow well. As z0 decreases,

there are fewer and fewer bound states, until finally (for z0 < /2,where the lowest odd state
disappears) only one remains. It is interesting
to note that there is always one bound state, no
matter how weak the well becomes.
Now moving on to scattering states where
E>0
the general solution as before is

We can use two of these to eliminate C and

D, and solve the remaining two for B and F :
B=i

F =

(x) = Aeikx + Beikx for (x < a) (124)

2mE
~

(125)

(x) = C sin(lx) + D cos(lx), for a < x < a

(126)
where as before
l

2m(E + V0 )
~

(134)

V02
= 1+
sin2
4E(E + V0 )

(136)

where n is an integer. The energies for perfect

transmission, then are given by

(127)

En + V0 =

n2 2 ~2
2m(2a)2

(137)

which happens to be the allowed energies for

the infinite square well

(128)

Here A is the incident amplitude, B is the reflected amplitude, and F is the transmitted amplitude.
There are four boundary conditions: Continuity of (x) at a says

Chapter 3: Formalism
The collection of all functions of x constitues
a vector space. To represent a possible physical
state, the wave function must be normalized :
Z

Aeika + Beika = C sin(la) + D cos(la) (129)

continuity of d/dx at a gives

||2 dx = 1

(138)

The set of all square-integrable functions,

on a specified interval

ik[Aeika Beika ] = l[C cos(la) + D sin(la)]

(130)
continuity of (x) at +a yields
C sin(la) + D cos(la) = F eika

+l
sin(2la)
cos(2la) i (k2kl

2a p
2m(En + V0 ) = n
~

To the right, assuming there is no incoming

wave in this region, we have
(x) = F eikx

e2ika A

(133)


2a p
T
2m(E + V0 )
~
(135)
Notice that T = 1 (the well becomes transparent) whenever the sine is zero, which is to
say, when
1

inside the well, where V (x) = V0 and the

general solution is

sin(2la) 2
(l k 2 )F
2kl

The transmission coefficient (T = |F |2 /|A|2 )

expressed in terms of the original variables, is
given by

where(as usual)
k

(132)

f (x) such that

|f (x)|2 dx <

(139)

this constitutes a (much smaller) vector space.

mathematicians call it L2 (a, b); physicist call it
Hilbert Space. In quantum mechanics, then

(131)
7

now the outcome of a measurement has got to

be real, and so, a fortiori, is the average of many
measurements:

Wave functions live in Hilbert Space

We define the inner product of two functions, f (x) and g(x), as follows
hf |gi

f (x) g(x)dx

hQi = hQi

(140)

But the complex conjugate of an inner product reverses the order

If f and g are both square-integrable (that

is, if they are both in Hilbert space),their inner
product is guaranteed to exist (the integral in
equation 140 converges to a finite number), This
follows from the integral Schwarz inequality

h|Qi
= hQ|i

i = hQf
|f i for all f (x)
hf |Qf

hf |f i =

|f (x)|2 dx 0

(150)

we call such operator hermitian

(142)

Observables are represented by hermitian operators

Determinate States

Moreover, the inner product of f (x) with itself,

Z

(149)

and this must hold true for any wave function

. Thus operators representing observables have
the verty special property that

Z
 sZ
Z b
 b

b


|f (x)|2 dx
|g(x)|2 dx
f (x) g(x)dx

 a

a
a
(141)
Notice in particular that
hg|f i = hf |gi

(148)

= q
Q

(143)

(151)

This is the eigenvalue equation for the op is an eigenfunction of Q,

and q is
erator Q;
the corresponding eigenvalue; thus

is real and non-negative; its zero only if

f (x) = 0
A function is said to be normalized if its
inner product with itself is 1; two functions are
orthogonal if their inner product is 0; and a set
of functions, {fn }, is orthonormal if they are
normalized and mutually orthogonal;

Determinate states are eigenfunctions of Q

n=1

Measurement of q on such a state is certain

to yield the eigenvalue q. The collection of all
eigenvalues of an operator is called its spectrum. Sometimes two (or more) linearly independent eigenfunctions share the same eigenvalue; in that case the spectrum is said to be
degenerate.
Eigenfunctions of Hermitian Operators
Discrete Spectra
Mathematically, the normalized eigenfunctions of a hermitian operato have two important
properties.
Theorem 1: Their eigenvalues are real.

if the functions {fn (x)} are orthonormal, the

coefficients are given by Fouriers trick

= qf
Qf

cn = hfn |f i

with eigen(i.e.,f (x) is an eigenfunction of Q,

value q), and

hfm |fn i = mn

(144)

Finally, a set of functions is complete if any

other function (in Hilbert space) can be expressed as a linear combination of them
f (x) =

cn fn (x)

(145)

(146)

Observables
The expectation value of an observable Q(x, p)
can be expressed very neatly in inner-product
notation:

hQi =

Qdx
= h|Qi

(152)

i = hQf
|f i
hf |Qf

(153)

qhf |f i = q hf |f i

(154)

then

(147)

and q must be real

8

Similarly, the expectation value Q should be

the sum over all possible outcomes of the eigenvalue times the probablity of getting that eigenvalue

Theorem 2: Eigenfunctions belonging to

distinct eigenvalues are orthogonal.
= qf,
Qf
so

= q g
and Qg

(155)

is hermitian. Then hf |Qgi

= hQf
|gi
and Q
q hf |gi = q hf |gi

hQi =

where cn = hfn |i

qn |cn |2

(162)

The momentum space wave function,

(p, t) is essentially the Fourier transform of the
position space wave function (x, t), which by
Plancherels theorem is its inverse Fourier transform.

(156)

again the inner product exist because the

eigenfunctions are in Hilbert space by assumption. but q is real so if q 6= q it must be that
hf |gi = 0.
Continuous Spectrum
If the spectrum of a hermitian operator is continuous, the eigenfunctions are not normalizable,
and the proofs of Theorems 1 and 2 fail, because
the inner products may not exist.
Generalized Statistical Interpretation
If you measure an observable Q(x, p) on a particle in the state (x, t), you are certain to get
one of the eigenvalues of the hermitian operator.
If the spectrum is dicrete, the probability of getting the particular eigenvalue qn associated with
the orthonormalized eigenfunction fn (x) is
|cn |2 ,

Z
1
eipx/~ (x, t)dx
2~
Z
1
(x, t) =
eipx/~ (p, t)dp
2~
(p, t) =

(163)
(164)
(165)

According to the generalized statistical interpretation, the probability that a measurement of

the momentum would yield a result in the range
dp is
|(p, t)|2 dp

(166)

The Uncertainty Principle

The generalized uncertainty principle is

(157)

If the spectrum is continuous, with real eigenvalues q(z) and associated Dirac orthonormalized eigenfunctions fz (x), the probability of getting result in the range dz is

2 2
A
B

2
1
h[A, B]i
2i

(167)

The energy-time uncertainty principle

|c(z)|2 dz,

where c(z) = hfz |i

(158)
i
d
hQi = h[H,
Q]i +
dt
~

The eigenfunctions of a hermitian operator

are complete, so that the wave function can be
written as a linear combination of them
(x, t) =

cn fn (x)

(159)

fn (x) (x, t)dx

|cn |2 = 1

(168)

= H
(169)
t
the Hamiltonian operator H is obtained from the
classical energy
i~

(160)

Of course, the total probability (summed over

all possible outcomes) has got to equal one
X

The generalization to three dimensions is

straightforward. Schrodingers equation says

Because the eigenfunctions are orthonormal,

the coefficients are given by Fouriers trick

cn = hfn |i =

Q
dt

Chapter 4: Quantum Mechanics in Three

Dimensions

1
1 2
mv 2 + V =
(p + p2y + p2z ) + V
2
2m x

(170)

by the standard prescription (applied now to

y and z, as well as x)

(161)

~
~
~
, py
, pz
i x
i y
i z

px

(r, , ) = R(r)Y (, )
(171)

(180)

,. The Angular Equation

or
~
p
i



Y
2Y
sin
+
= l(l + 1) sin2 Y

2
(181)
you might recognize this equation, it occurs
in the solution to Laplaces equation in classical
electrodynamics. as always, we try seperation of
variables

sin

(172)

thus
i~

~2 2
=
+V
t
2m

(173)

where
2
2
2

+
+
x2
y 2
z 2
2

Y (, ) = ()()
(174)

plugging this in and deviding by gives us

two solutions

is the Laplacian, in cartesian coordinates.

The potential V and the wave function are
now functions of r = (x, y, z) and t.
the normalization condition reads
Z

||2 d3 r = 1




1
d
d
sin
sin
+ l(l + 1) sin2 = m2

d
d
(183)

(175)

1 d2
= m2
d2

with the integral taken over all space. if the

potential is independent of time, there will be a
complete set of stationary states
n (r, t) = n (r)eiEn t/~

~2 2
+ V = E
2m

(184)

The equation is easy

d2
= m2 () = eim
d2

(176)

where the spatial wave function n satisfies

the time-independent Schrodinger

(182)

(185)

Now when advances by 2, we return to the

same point in space, so it is natural to require
that

(177)

The general solution to the time-dependent

Schrodinger equation is

( + 2) = ()

(186)

from this it follows that m must be an integer

(r, t) =

cn n (r)eiEn t/~

(178)

m = 0, 1, 2, ....

Seperation Of variables Typically, the potential is a function only of the distance from
the origin. In that case it is natural to adopt
spherical coordinates, (r, , ). In spherical
coordinates the Laplacian takes the form

2 =

1
r2 r

(187)

The equation is not so simple, the solution

is
() = APlm (cos )

(188)

where Plm is the associated Legendre function, defined by






r2
+ 2
sin
r
r sin

 2 

1
(179)
+ 2 2
r sin 2

Plm (x)

We begin by looking for solutions that are

seperable by products

2 |m|/2

(1 x )

d
dx

|m|

Pl (x)

(189)

and Pl (x) is the lth Legendre polynomial,

defined by the Rodrigues formula
10

1
2l l!

Pl (x)

d
dx

l

(x2 1)l

this is as far as we can go until a specific potential V (r) is provided.

The infinite spherical well

(190)

V (r) =

Now, the volume element in spherical coordinates is

3

d r = r sin drdd

(191)

|R|2 r2 dr = 1

(193)

|Y |2 sin dd = 1

(194)

(2l + 1) (l |m|)! im m
e
Pl (cos )
4 (l + |m|)!
(195)
m
where = (1) for m 0 and = 1 for
m 0. As we shall prove later on, they are
automatically orthogonal.
The Radial Equation Notice that the angular part of the wave function, Y (, ), is the
same for all spherically symmetric potentials; the
actual shape of the potential ,V (r), affects only
the radial part of the wave function,R(r), which
is determined by
=

u(r) rR(r)

En0 =

n2 2 ~2
, (n = 1, 2, 3, ...)
2ma2

(203)

(204)

where jl (x) is the spherical Bessel function

pf order l, and nl (x) is the spherical Neumann
function of order l. They are defined as follows

(196)
jl (x) (x)l

nl (x) (x)l

1 d
x dx

l

1 d
x dx

sin x
x

l

cos x
x

(205)

(206)

Notice that the Bessel functions are finite at

the origin, but Neumann functions blow up at
the origin. Accordingly, we must have Bl = 0,
and hence

the normalization condition becomes

|u|2 dr = 1

(201)

u(r) = Arjl (kr) + Brnl (kr)



~2 l(l + 1)
~2 d2 u
u = Eu (197)
+
V
+

2m dr2
2m r2

2mE
k
~

the same as for the one-dimensional infinite

square well. The general solution to equation
200 (for an arbitrary integer l) is not as familiar

using this relationship we can now write the

radial equation as

(200)

d2 u
= k 2 u u(r) = A sin(kr) + B cos(kr)
dr2
(202)
we must choose B = 0 because r 0 the
radial wave function blows up. The boundary
condition then requires sin(ka) = 0, and hence
ka = n, for some integer n. The allowed energies are evidently

The normalized angular wave functions are

called spherical harmonics

Ylm (, )



d2 u
l(l + 1)
2
u
=

k
dr2
r2

as usual. Our problem is to solve this equation, subject to the boundary condition u(a) =
0. The case l = 0 is easy

It is convenient to normalize R and Y separately

(199)

where

||2 r2 drdd =
Z
Z
|R|2 r2 dr |Y |2 sin dd = 1 (192)

0, ifra
, ifr>a

Outside the well, the wave function is zero;

inside the well, the radial equation says

so the normalization condition becomes

Z

(198)
11

so that
R(r) = Ajl (kr)

(207)


d2 u
0
l(l + 1)
u
= 1
+
d2

There remains the boundary condition, R(a) =

0. Evidently k must be chosen such that
jl (ka) = 0

(208)

Next we examine the asymptotic form of the

solutions. As , the constant term in the
brackets dominate, so approximately

(209)

d2 u
=u
d2

the boundary condition requires that

k=

1
nl
a

where nl is the nth zero of the lth spherical

Bessel function. The allowed energies then, are
given by
~
2
2ma2 nl

u() = Ae + Be

u() Ae

d2 u
l(l + 1)
=
u
d2
2

The Hydrogen Atom

u() = Cl+1 + Dl

e 1
40 r

u() Cl+1

u() = l+1 e v()

v() =

(214)

1 d u
1
me
l(l + 1)
u
= 1
+
2
2
2
k dr
20 ~ k (kr)
(kr)2
(215)
This suggest that we introduce
me2
20 ~2 k

cj j

(225)

j=0

cj+1 =

kr and 0

(224)

Finally, we assume the solution, v(), can be

expressed as a power series in

dividing equation 213 by E gives

2

(223)

The next step is to peel off the asymptotic

behaviour, introducing the new function v()



e2 1
~2 l(l + 1)
~2 d2 u
u = Eu
+
+

2m dr2
40 r
2m r2
(213)
our problem is to solve this equation for u(r),
and determine the allowed energies. Our first
task is to tidy up the notation. Let

k 2 ~2
2mE
E=
k
~
2m

(222)

let D = 0, because l blows up as 0,

thus

(212)

and the radial equation says

(221)

the general solution is

From Coulombs law, the potential energy is

(220)

for large . On the other hand, as 0 the

centrifugal term dominates, approximately then

(211)

with the constant Anl to be detemined by normalization.

V (r) =

(219)

but e blows up ( as ), so B = 0,
evidently

(210)

and the wave functions are

nlm (r, , ) = Anl (nl r/a)Ylm (, )

(218)

The general solution is

Enl =

(217)

2(j + l + 1) 0
(j + 1)(j + 2l + 2)

cj

(226)

This recursion formula determines the coefficients, and hence the function v(). Now lets
see what the coefficients look like for large j (this
corresponds to large , where the higher power
dominate . In this regime the recursion formula
says

(216)
12

2j
2
cj =
cj
j(j + 1)
j+1

cj+1
=

(227)

40 ~2
= 0.529x1010m
me2

is called the Bohr radius. it follows that

suppose for a moment that this were exact.

Then

=
2j
cj = c0
j!

(228)

X
2j
j=0

j!

r
an

(239)

The spatial wave functions for hydrogen are

labeled by three quantum numbers (n, l, andm)

so
v() = c0

(238)

nlm (r, , ) = Rnl (r)Ylm (, )

(229)

(240)

and

and hence
u() = c0

l+1

Rnl (r) =

(230)

cj+1 =

(231)

(and beyond which all coefficients vanish automatically). equation 226 becomes
2(jmax + l + 1) 0 = 0

(232)

n jmax + l + 1

(233)

(241)

and v() is a polynomial of degree jmax =

n l 1 in , whose coefficients are determined
by the recursion formula

which blows up at large . The series must

terminate. There must occur some maximal integer, jmax such that
cjmax +1 = 0

1 l+1
e v()
r

2(j + l + 1 n
cj
(j + 1)(j + 2l + 2)

(242)

The polynomial v() is a function well known

to mathematicians; apart from normalization, it
can be written as
v() = L2l+1
nl1 (2)

Defining

(243)

where
(the so-called principal quantum number), we have
0 = n

Lpqp (x) (1)p

d
dx

But 0 determines E
E=

Lq (x) e

me
k ~
= 2 2 2 2
2m
8 ~ 0

(235)

m
En =
2~2

e2
4

2 #

1
E1
= 2 n = 1, 2, ..
2
n
n
(236)
This is the famous Bohr Formula. combining equation 216 and 234 we get
k=

me
40 ~2

1
1
=
n
an

(244)

d
dx

q

(ex xq )

(245)

is the qth Laguerre polynomial, the normalized hydrogen wave functions are

so the allowed energies are

"

Lq (x)

is an associated Laguerre polynomial,

and

(234)

2 2

p

nlm =

s

3
 l
(n l 1)!
2r
2
e
r/na
na
2n[(n + l)!]3
na
 2l+1

Lnl1 (2r/na) Ylm (, ) (246)

The spectrum of Hydrogen

An electron may undergo a transition to
some other energy state, either by absorbing energy or emmiting energy, the difference in energy
between the initial and final states are

(237)

where
13

Y = Ei Ef == 13.6eV

1
1
2
2
ni
nf

[L2 , Lx ] = 0, [L2 , Ly ] = 0, [L2 , Lz ] = 0 (255)

(247)

or, more compactly,

Now, according to the Planck formula, the

energy of a photon is proportional to its frequency
E = hv

[L2 , L] = 0

So L2 is compatibale with each component of

textbfL, and we can hope to find simultaneous
eigenstates of L2 and (say) Lz

(248)

Meanwhile, the wavelength is given by =

c/v, so
1
=R

1
1
2
n2f
ni

L2 f = f and Lz f = f

(257)

Well use a ladder operator technique, Let

(249)

L Lx iLy

where

m
R
4c~3

(256)

(258)

The commutator with Lz is



e2
40

2

= 1.097 10 m

(250)

(259)

[Lz , L ] = ~L

(260)

so

is know as the Rydberg constant

Angular Momentum
Classically, the angular momentum of a particle (with respect to the origin) is given by the
formula
L=rp

[Lz , L ] = ~(Lx iLy )

And of course,
[L2 , L ] = 0

(261)

I claim that if f is an eigenfunction of L2 and

Lz , so also is L f equation 261 says

(251)

which is to say
L2 (L f ) = L (L2 f ) = L (f ) = (L f )
(262)
2
so if L f is an eigenfunction of L , with the
same eigenvalue , and equation 260 says

Lx = ypz zpy , Ly = zpx xpz , Lz = xpy ypx

(252)
The corresponding quantum operators are
obtained by the standard prescription px
i~/x etc.
Eigenvalues
The operators Lx and Ly do not commute; in
fact

Lz (L f ) = (Lz L L Lz ) + L Lz f = ~L + L (f )
(263)
= ( ~)(L f )

so L f is an eigenfunction of Lz , with the

new eigenvalue ~. we call L+ the raising
operator, because it increases the eigenvalue of
Lz by ~, and L the lowering operator, because
it lowers the eigenvalue by ~. When using the
raising operator we will eventually reach a state
for which the z-component exceeds the total

[Lx , Ly ] = i~Lz , [Ly , Lz ] = i~Lx , [Lz , Lx ] = i~Ly

(253)
Notice that Lx , Ly , and Lz are incompatible
observables and it would therefore be futile to
look for states that are simultaneously eigenfunctions of Lx and Ly . On the other hand, the
square of the total angular momentum
L2 L2x + L2y + L2z

(264)

L ft = 0

(265)

let ~l be thje eigenvalue of Lz at this top rung.

(254)

Lz ft = ~lft ; L2 ft = ft

does commute with Lx

14

(266)

Now,
L L = L2 L2z i(i~Lz )

= (cos cos )i + (cos sin )j (sin )k

(276)
= (sin )i + (cos )j
(277)

(267)

or putting it the other way around

L2 = L L + L2z ~Lz

(268)

Evidently

it follows that



~
sin
cos cot
i



~

Ly =
+ cos
sin cot
i

Lx =
2

L ft = (L L+ +

L2z

+ ~Lz )ft = ~ l(l + 1)ft

(269)

and nence
= ~2 l(l + 1)

and
Lz =

l = 0, 1/2, 1, 3/2, ...; m = l, l + 1, ..., l 1, l

(272)
Eigenfunctions
First of all we need to rewrite Lx , Ly , and Lz
in spherical coordinates. Now, L=(~/i)(r ) ,
and the gradient, in spherical coordinates, is

1
sin





1
2
2
2
+ V = E
r
+
L
~
2mr2
r
r
(283)
Spin
In classical mechanics, a rigid object admits
two kinds of angular momentum: orbital (L =
r p), associated with the motion of the center
of mass, and spin (S = I) , associated with
motion about the center of mass. The algebraic
theory of spin is a carbon copy of the theory of
orbital angular momentum, beggining with the
fundamental commutation relations

(273)



~

L=
r(
r r)
+ (
r )
+ (
r )
i
r

sin
(274)

But (
r r) = 0, (
r ) = , and (
r ) =
and hence



sin

H = E, L2 = ~2 l(l + 1), Lz = ~m
(282)
incidentally, we can use equation 281 to
rewrite the Schrodinger equation

meanwhile, r=r
r, so

~
i

(280)





1 2
sin
+

sin2 2
(281)
conclusion: Spherical harmonics are eigenfunctions of L2 and Lz . When we solved the
Schrodinger equation by seperation of variables,
we were inadvertently constructing simultaneous
eigenfunctions of the three commuting operators
H, L2 , and Lz
L2 = ~2

where

L=

~
i

using the raising and lowering operators we

find

L2 flm = ~2 l(l + 1)flm ; Lz flm = ~mflm (271)

1
1
+
+
r
r
r sin

(279)

(270)

This tells us the eigenvalue of L2 in terms of

the maximum eigenvalue of Lz . Evidently the
eigenvalues of Lz are m~, where m goes from l
to l in N integer steps. In particular, it follows
that l = l+N , and hence l = N/2, so l must be
an integer or a half-integer. The eigenfunctions
are characterized by the numbers l and m

= r

(278)

(275)

The unit vectors and can be resolved into

their cartesian components

[Sx , Sy ] = i~Sz , [Sy , Sz ] = i~Sx , [Sz , Sx ] = i~Sy

(284)
15

it follows that the eigenvectors of S 2 and Sz

satisfy
2

Similarly

Sz + =

S |smi = ~ s(s + 1)|smi; Sz |smi = ~m|smi

(285)
and

~
~
+ , Sz =
2
2

from which it follows that

Sz =

p
S |smi = ~ s(s + 1) m(m 1)|s(m 1)i
(286)
where S Sx iSy . But this time the eigenfunctions are not spherical harmonics , and there
is no apriori reason to exclude the half-integer
values of s and m:

 
1
0

S+ = ~





~ 0 1
~ 0 i
Sx =
, Sy =
2 1 0
2 i 0



3 2 1 0
~
4
0 1

(297)







0 1
0 i
1 0
x
, y
, z
1 0
i 0
0 1
(298)
These are the famous Pauli spin matrices.
The eigenspinors of Sz are (of course)

(288)

(289)
  
1
, eigenvalue +
0
  
0
=
, eigenvalue
1
+ =

(290)


~
2

~
2

(299)
(300)

If you measure Sz on a particle in the general

state (equation 288), you could get +~/2, with
probability |a|2 , or ~/2, with probability |b|2 .
Since they are the only possibilities
|a|2 + |b|2 = 1

(291)

(301)

(i.e, the spinor must be normalized ). But

what if instead, you chose to measure Sx ? What
are the possible results. According to the generalized statistical interpretation, we nee dto know
the eigenvalues and eigenspinors of Sx , the characteristic equation is

we can write S2 in matrix for as

S2 =

(296)

Since Sx , Sy , and Sz all carry a factor of ~/2,

it is tidier to write S=(~/2), where

for spin down. Meanwhile, the spin operators

become 22 matrices, which we can work out by
noting their effect on + and .Equation 285
says
3
3
S2 + = ~2 + and S2 = ~2
4
4





0 1
0 0
, S = ~
0 0
1 0

Now S = Sx iSy , so Sx = (1/2)(S+ + S )

and Sy = (1/2i)(S+ S ), and hence

representing spin up, and

 
0
=
1

(294)

S+ = ~+ , S + = ~ , S+ = S = 0
(295)
so

with
+ =



~ 1 0
2 0 1

Meanwhile, equation 286 says

3
1
s = 0, , 1, , ...; m = s, s + 1, ..., s 1, s.
2
2
(287)
Pi mesons have spin 1/2; photons have spin 1;
deltas have spin 3/2; gravitons have spin 2; and
so on.
Spin 1/2
By far the most important case is s = 1/2, for
this is the spin of the particles that make up ordinary matter( protons, neutrons, and electrons),
as well as quark and leptons. The general state
of a spin-1/2 particle can be expressed as a twoelement column matrix (or spinor);
 
a
=
= a+ + b
b

(293)

(292)
16



 ~/2


~ 2
~
2


~/2  = 0 = 2 2
Not suprisingly, the possible values for Sx are
the same as those for Sz . The normalized eigenspinors of Sx are

The Hamiltonian, in matrix form, is



B0 ~ 1 0
H = B0 Sz =
2
0 1

(309)

The eigenstates of H are the same as those of

(x)
+

(x)

1
  
2 , eigenvalue +
=
1

2
1
  
2 , eigenvalue
=
1

Sz
~
2

(302)

~
2

(303)

+ , with energy E+ = (B0 ~)/2

, with energy E = +(B0 ~)/2

since the Hamiltonian is time-independent,

the general solution to the time-dependent
Schrodinger equation is

= H
(310)
t
can be expressed in terms of the stationary
states
i~

As the eigenvectors of a hermitian matrix,

they span the space; the generic spinor (equation 288) can be expressed as a linear combination of them

aeiB0 t/2
(t) = a+ e
+b e
=
beiB0 t/2
(311)
The constants a and b are determined by the
initial conditions
iE+ t/~

a+b

(x)

+ +

ab

(x)

(304)

If you measure Sx , the probability of getting

+~/2 is (1/2)|a + b|2, and the probability of getting ~/2 is (1/2)|a b|2 .
Electron in a Magnetic Field
A spinning charged particle constitutes a
magnetic dipole. Its magnetic dipole moment,, is proportional to its spin angular momentum, S:
= S

(0) =

(t) =

(312)

cos(/2)eiB0 t/2
sin(/2)eiB0 t/2

(313)

hSx i = (t) Sx (t) = (cos(/2)eiB0 t/2 sin(/2)eiB0 t/2 )




cos(/2)eiB0 t/2
~ 0 1

2 1 0 sin(/2)eiB0 t/2
~
= sin cos(B0 t) (314)
2

(306)

similarly,
~
hSy i = (t) Sy (t) = sin sin(B0 t)
2
(315)
and

(307)

Larmor preccesion: Imagine a particle of

spin 1/2 at rest in a uniform magnetic field,
which points in the z direction
B = B0 k

To get a feel for whats happening here, lets

calculate the expectation value of S, as a function of time

(305)

so the Hamiltonian of a spinning charged particle, at rest in a magnetic field B is

H = B S

 
a
b

With no essential loss of generality I will write

a = cos(/2) and b = sin(/2), Thus

the proportionality constant, , is called the

gyromagnetic ratio. When a magnetic dipole
is placed in a magnetic field B, it experiences a
tourqe, x B which tends to line it up parallel to
the field. The energy associated with this tourqe
is
H = B

iE t/~

hSz i = (t) Sy (t) =

(308)
17

~
cos
2

(316)

|11i =
|10i = 12 ( + )
s = 1 (triplet)

|1 1i =
This is called the triplet combination, for the
obvious reason. Meanwhile, the orthogonal state
with m = 0 carries s = 0;

Evidently hSi is tilted at a constant angle

to the z axis, and precesses about the field at the
Larmor frequency
= B0

(317)

Just as it would classically

Addition of Angular Momenta
Suppose now that we have twofor e spin-1/2
particlesfor example, the electron and the proton in the ground state of hydrogen. Each can
have spin up or spin down so there are four possibilities in all
, , ,



1
|00i = ( ) s = 0 (singlet) (324)
2
(if you apply the raisong or lowering operator
to this state, youll get zero
I need to prove that the triplet states are
eigenvectors of S 2 with eigenvalue 2~2 , and the
singlet is an eigenvector of S 2 with eigenvalue 0.
Now,

(318)

where the first row refers to the electron and

the second row to the proton. Question: What
is the total angular momentum of the atom? Let
(1)

SS

(2)

+S

S 2 = (S(1) + S(2) ) (S(1) + S(2)

(319)

= (S (1) )2 + (S (2) )2 + 2S(1) S(2)

Each of these four composite states is an

eigenstate of Sz the z-components simply add

(325)
(326)

Using equations 294 and 297, we have

Sz 1 2 = (Sz(1) +Sz(2) )1 2 = (Sz(1) chi1 )2 +1 (Sz(2) 2 ) S(1) + S(2) () = (Sx(1) )(Sx(2) )

= (~m1 1 )2 +1 (~m2 2 ) = ~(m1 +m2 )1 2
+ (Sy(1) )(Sy(2) ) + (Sz(1) )(Sz(2) )

 



(320)
~
i~
i~
~

)
=
2
2
2
2
So m (the quantum number of the composite



~
~
system) is just m1 + m2
+
)
)
2
2
~2
=
(2 ) (327)
: m = 1;
4
: m = 0;
similarly
: m = 0;
: m = 1
~2
(2 )
(328)
S(1) + S(2) () =
At first galnce, this doesnt look right: m is
4
supposed to advance in integer steps , from s
It follows that
to +s, so it appears that s = 1 but there is an
extra state with m = 0. One way to untangle
this problem is to apply the lowering operator,
~2 1
~2
(1)
(2)
(2 +2 ) =
S(1) S(2) |10i =
|10i
S = S + S to the state , using equation
4 2
4
296
(329)
and
S () =

(1)
(S

) +

(2)
(S

= (~ ) + (~ )
= ~( + )

(321)
~2 1
3~2
(2 2 + ) =
|00i
4 2
4
(330)
Returning to equation 325-326 ( and using
equation 291), we conclude that

(322)

S(1) S(2) |00i =

(323)

Evidently the three states with s = 1 are (in

the notation |s mi):
18

S 2 |10i =

S 2 |00i =

3~2
3~2
~
+
+2
4
4
4

3~2
3~2
3~
+
2
4
4
4


2

The statistical interpretation carries over in

the obvious way
|10i = 2~2 |10i


2

|(r1 , r2 , t)|2 d3 r1 d3 r2

(331)

is the probability of finding particle 1 in the

volume d3 r1 and particle 2 in the volume d3 r2 ;
evidently must be normalized in such a way
that

|00i = 0 (332)

What we have just done (combining spin 1/2

with spin 1/2 to get spin 1 and spin 0) is the simplest example of a larger problem: if you combine spin s1 with spin s2 , what total spins s can
you get? The answer is that you get every spin
from (s+ s2 ) down to (s1 s2 ) or (s2 s1 ), if
s2 > s1 in integer steps

|smi =

m1 +m2 =m

(r1 , r2 , t) = (r1 , r2 )eiEt /~

(342)

(r1 , r2 ) = A[a (r)b (r) b (r)a (r)] (343)

(335)

Its time evolution is deterimed (as always) by

the Schrodinger equation:

Thus the theory admits to kinds of identical

particles: bosons, for which we use the plus
sign , and fermions, for which we use the minus
sign. Photons and mesons are bosons; protons
and electrons are fermions. It so happebns that
(
all particles with integer spin are bosons, and
all particles with half-integer spin are fermions

(336)

Where H is the Hamiltonian for the whole

system

H =

(341)

Quantum mechanics neatly accomidates the

existance of particles that are indistinguishable
in principle: We simply construct a wave function that is non committal as to which particle
is in which state. there are actually two ways to
do it

Two-Particle System
The state of a two-particle system is a function of the coordinates of particle one (r1 ), the
coordinates of particle two (r2 ), and the time

~2 2
~2 2
1
+ V = E
2m1
2m2 2

(r1 , r2 ) = a (r)b (r)

Chapter 5: Identical Particles

= H
t

(340)

and E is the total energy of the system

Bosons and Fermions
Suposse particle 1 is in the (one-particle) state
a (r), and particle 2 is in the state b (r). (ignoring spin at the moment). In that case (r1 , r2 )
is a simple product

(because the z components add, the only composite states that contribute are those for which
m1 + m2 = m). The triplet combination and
the singlet are special cases of this general form,
with s1 = s2 = 1/2 I used the notation = | 12 21 i,
s1 s2 s
are called
= | 12 ( 12 )i. The constants Cm
1 m2 m
Clebsch-Gordan coefficients.

i~

(339)

where the spatial wave function () satisfies

the time-independent Schrodinger equation

s1 s2 s
Cm
|s1 m1 i|s2 m2 i (334)
1 m2 m

(r1 , r2 , t)

|(r1 , r2 , t)|2 d3 r1 d3 r2 = 1

For time-independent potentials, we obtain a

complete set of solutions by seperation of variables

s = (s1 +s2 ), (s1 +s2 1), (s1 +s2 2), ..., |s1 s2 |
(333)
The combined state |smi with total spin s and
z-component m will be some linear combination
of the composite states |s1 m1 i|s2 m2 i
X

(338)

It follows, in paticular, that two identical

fermions cannot occupy the same state. For if
a = b , then

~
~
2
2 + V (r1 , r2 , t) (337)
2m1 1 2m2 2
19

1
(x1 , x2 ) = [a (x1 )b (x2 ) b (x1 )a (x2 )]
2
(350)
Lets calculate the expectation value of the
square of the separation distance between the
two particles

(r1 , r2 ) = A[a (r)a (r) a (r)a (r)] = 0

(344)
This is the famous Pauli exclusion principle. I assumed, for the sake of argument, that
one particle was in the state a and the other in
state b , but there is a more general way to formulate the problem. Let us define the exchange
operator, P , which interchanges the two particles
P f (r1 , r2 ) = f (r1 , r2 )

h(x1 x2 )2 i = hx21 i + hx22 i 2hx1 x2 i

Case 1: Distinguishable particles. For

the wave function in equation 348

(345)

Clearly P 2 = 1, and it follows that the eigenvalues of P are 1. Now, if the two particles are
identical, the Hamiltonian must treat them the
same: m1 = m2 and V (r1 , r2 ) = (r2 , r1 ) . It follows that P and H are compatible observables,
[P, H] = 0

hx21 i =

(346)

hx22 i =

x21 |a (x1 )|2 dx1

|a (x1 )|2 dx1

|b (x2 )|2 dx2 = hx2 ia

(352)

x22 |b (x2 )|2 dx2 = hx2 ib

(353)

and

hx1 x2 i =

x1 |a (x1 )|2 dx1

x2 |b (x2 )|2 dx2 = hxia hxib

(354)

in this case then

(347)

The symmetrization requirement states

that, for identical particles, the wave function is
not merely alllowed, but required to satisfy equation 347. This is the general statement, of which
equation 343 is a special case.
Exchange Forces
To give some sense of what the symmetrization requirement does, we can suppose that one
particle is in state a (x), and the other is in
state b (x), and these two states are orthogonal
and normalized. If the two particles are distinguishable, and number 1 is in state a , then the
combined wave function is
(x1 , x2 ) = a (x1 )b (x2 )

and

and hence we can find a complete set of functions that are simultaneously eigenstates of both.
That is to say, we can find solutions to the
Schrodinger equation that are either symmetric
(eigenvalue + 1) or antisymmetric (eigenvalue 1) under exchange
(r1 , r2 ) = (r1 , r2 )

(351)

h(x1 x2 )2 id = hx2 ia + hx2 ib 2hxia hxib (355)

Case 2: Identical particles. For the wave
function in equations 349 and 350
Z
Z
1
( x21 |a (x1 )|2 dx1 |b (x2 )|2 dx2
2
Z
Z
+ x21 |b (x1 )|2 dx1 |a (x2 )|2 dx2
Z
Z
x21 a (x1 ) b (x1 )dx1 b (x2 ) a (x2 )dx2
Z
Z
x21 b (x1 ) a (x1 )dx1 a (x2 ) b (x2 )dx2 )
hx21 i =

(348)

if they are identical bosons, the composite

wave function is

 1
1 2
hx ia + hx2 ib 0 0 =
hx2 ia + hx2 ib
2
2
(356)

1
+ (x1 , x2 ) = [a (x1 )b (x2 ) + b (x1 )a (x2 )]
2
(349)
and if they are identical fermions

similarly
hx22 i =
20

1
hx2 ib + hx2 ia
2

(357)

(naturally, hx22 i = hx21 i, since you cant tell

them apart.) But

(naturally, hx22 i = hx21 i, since you cant tell

them apart.) But

Z
Z
1
2
hx1 x2 i = ( x1 |a (x1 )| dx1 x2 |b (x2 )|2 dx2
2
Z
Z
+ x1 |b (x1 )|2 dx1 x2 |a (x2 )|2 dx2
Z
Z

x1 a (x1 ) b (x1 )dx1 x2 b (x2 ) a (x2 )dx2

Z
Z
x1 b (x1 ) a (x1 )dx1 x2 a (x2 ) b (x2 )dx2 )

Z
Z
1
2
hx1 x2 i = ( x1 |a (x1 )| dx1 x2 |b (x2 )|2 dx2
2
Z
Z
+ x1 |b (x1 )|2 dx1 x2 |a (x2 )|2 dx2
Z
Z

x1 a (x1 ) b (x1 )dx1 x2 b (x2 ) a (x2 )dx2

Z
Z
x1 b (x1 ) a (x1 )dx1 x2 a (x2 ) b (x2 )dx2 )

1
(hxia hxib + hxib hxia hxiab hxiba hxiba hxiab )
2
= hxia hxib |hxiab |2 (358)

1
(hxia hxib + hxib hxia hxiab hxiba hxiba hxiab )
2
= hxia hxib |hxiab |2 (364)

where

where

psia (x1 )| dx1

x22 |b (x2 )|2 dx2

hxiab

= hx ib (359)

xa (x) b (x)dx

(365)

Evidently

and

hx1 x2 i =

x1 |a (x1 )|2 dx1

h(x1 x2 )2 i = hx2 ia +hx2 ib 2hxia hxib 2|hxiab |2

(366)
x2 |b (x2 )|2 dx2 = hxia hxib
comparing equations 355 and 360, we see that
(360)
the difference resides in the final term

in this case then

h(x)2 i = h(x)2 id 2|hxiab |2

h(x1 x2 ) id = hx ia + hx ib 2hxia hxib (361)

(367)

Atoms
A neutral atom, of atomic number Z, consists
of a heavy nucleus, with electric charge Ze, sorrounded by Z electrons (mass m and charge e).
The Hamiltonian for this system is

Case 2: Identical particles. For the wave

function in equations 349 and 350

Z
Z
1
2
2
= ( x1 |a (x1 )| dx1 |b (x2 )|2 dx2
2
Z
Z
+ x21 |b (x1 )|2 dx1 |a (x2 )|2 dx2
Z
Z
2

x1 a (x1 ) b (x1 )dx1 b (x2 ) a (x2 )dx2

Z
Z
x21 b (x1 ) a (x1 )dx1 a (x2 ) b (x2 )dx2 )
hx21 i




Z 
X
~2 2
Ze2
1

H=

2m j
40
rj
j=1
1
+
2

 1
1 2
hx ia + hx2 ib 0 0 =
hx2 ia + hx2 ib
2
2

similarly


1
hx2 ib + hx2 ia
2

1
40

X
Z
j6=k

e2
|rj rk |

(368)

The term in the curly brackets represents the

kinetic plus potential of the jth electron, in the
electric field of the nucleus; the secon sum (which
runs over all values of j and k except j = k) is the
potential associated with the multual repulsion
of the electrons. (the factor of 1/2 in front corresponds that the summation counts each pair
twice. The problem is to solve Schrodingers
equation

(362)

hx22 i =

(363)
21

H = E

The Free Electron Gas

Suppose the object in question is a rectangular solid, with dimensions lx , ly , lz , and imagine
that an electron inside experiences no force at
all, except at the impenetrable walls
(
0, if0 < x < lx , 0 < y < ly , and0 < z < lz
V (x, y, z) =
, otherwise

(369)

for the wave function (r1 , r2 , ...rZ ). Because

electrons are identical fermions, however, not all
solutions are acceptable;only those for which the
complete state (position and spin)
(r1 , r2 , ...rZ )(s1 , s2 , ...sZ )

(370)

The Schrodinger equation,

is antisymmetric with respect to interchange

of any two electrons. In particular, no two electrons can occupy the same state
Helium
After hydrogen, the simplest atom is helium
(Z = 2). The Hamiltonian,



1 2e2
~2 2

H=
2m 1 40 r1


~2 2
1 2e2
+

2m 2 40 r2
e2
1
+
40 |r1 r2 |

~2 2
= E
2m

(376)

separates, in cartesian coordinates: (x, y, z) =

X(x)Y (y)Z(z), with
~2 dX 2
= Ex X
2m dx2
2
2
~ dY
= Ey Y

2m dy 2
~2 dZ 2

= Ez Z
2m dz 2

(377)
(378)
(379)

and E = Ex + Ey + Ez . Letting

(371)

2mEy
2mEx
2mEz
kx
, ky
, kz
~
~
~
(380)
we obtain the general solutions

consists of two hydrogenic Hamiltonians (with

nuclear charge 2e), one for each electron 1 and 2,
together with the final term describing the repulsion of the two electrons. It is this last term that
causes all the the trouble. If we simply ignore it,
the Schrodinger equation sperates, and the solutions can be written as products of hydrogen
wave functions

X(x) = Ax sin(kx x) + Bx cos(kx x)

(381)

Y (y) = Ay sin(ky y) + Bx cos(ky y)

Z(z) = Az sin(kz z) + Bx cos(kz z)

(382)
(383)

(372)

(384)

only with half the Bohr radius and four times

the Bohr energies. The total energy would be

The boundery conditions require X(0) =

Y (0) = Z(0) = 0, so Bx = By = B + z = 0,
and X(lx ) = Y (ly ) = Z(lz ) = 0, so that

(r1 , r2 ) = nlm (r1 )n l m (r2 )

E = 4(En + En )

(373)
kx lx = nx , ky ly = ny , kz lz = nz

where En = 13.6/n2 eV. In particular, the

ground state would be

0 (r1 , r2 ) = 100 (r1 )100 (r2 ) =

where each n is a positive integer

8 2(r1 +r2 )/a

e
a3
(374)

nx = 1, 2, 3, .., ny = 1, 2, 3, .., nz = 1, 2, 3, ..
(386)
The normalized wave functions are

and its energy would be

E0 = 8(13.6 eV) = 109 eV

(385)

(375)

nx ny nz =

Solids
22

8
sin
lx ly lz






nx
ny
nz
x sin
y sin
z
lx
ly
lz
(387)

hxiab

xa (x) b (x)dx

(388)



1 2e2
~2 2

H=
2m 1 40 r1


~2 2
1 2e2
+

2m 2 40 r2
1
e2
+
40 |r1 r2 |

Evidently

h(x1 x2 )2 i = hx2 ia +hx2 ib 2hxia hxib 2|hxiab |2

(389)
comparing equations 355 and 360, we see that
the difference resides in the final term

h(x)2 i = h(x)2 id 2|hxiab |2

consists of two hydrogenic Hamiltonians (with

nuclear charge 2e), one for each electron 1 and 2,
together with the final term describing the repulsion of the two electrons. It is this last term that
causes all the the trouble. If we simply ignore it,
the Schrodinger equation sperates, and the solutions can be written as products of hydrogen
wave functions

(390)

Atoms
A neutral atom, of atomic number Z, consists
of a heavy nucleus, with electric charge Ze, sorrounded by Z electrons (mass m and charge e).
The Hamiltonian for this system is

(r1 , r2 ) = nlm (r1 )n l m (r2 )

1
40

X
Z
j6=k

e2
|rj rk |

E = 4(En + En )
(391)

0 (r1 , r2 ) = 100 (r1 )100 (r2 ) =

8 2(r1 +r2 )/a

e
a3
(397)

and its energy would be

E0 = 8(13.6 eV) = 109 eV

(398)

Solids
The Free Electron Gas
Suppose the object in question is a rectangular solid, with dimensions lx , ly , lz , and imagine
that an electron inside experiences no force at
all, except at the impenetrable walls
(
0, if 0 < x < lx , 0 < y < ly , and 0 < z < lz
V (x, y, z) =
, otherwise

(392)

for the wave function (r1 , r2 , ...rZ ). Because

electrons are identical fermions, however, not all
solutions are acceptable;only those for which the
complete state (position and spin)
(r1 , r2 , ...rZ )(s1 , s2 , ...sZ )

(396)

where En = 13.6/n2 eV. In particular, the

ground state would be

The term in the curly brackets represents the

kinetic plus potential of the jth electron, in the
electric field of the nucleus; the secon sum (which
runs over all values of j and k except j = k) is the
potential associated with the multual repulsion
of the electrons. (the factor of 1/2 in front corresponds that the summation counts each pair
twice. The problem is to solve Schrodingers
equation
H = E

(395)

only with half the Bohr radius and four times

the Bohr energies. The total energy would be




Z 
X
Ze2
1
~2 2

H=
2m j
40
rj
j=1
1
+
2

(394)

(393)

The Schrodinger equation,

is antisymmetric with respect to interchange

of any two electrons. In particular, no two electrons can occupy the same state
Helium
After hydrogen, the simplest atom is helium
(Z = 2). The Hamiltonian,

~2 2
= E
2m

(399)

separates, in cartesian coordinates: (x, y, z) =

X(x)Y (y)Z(z), with
23

3
3
=
lx ly lz
V

~ dX
= Ex X
2m dx2
2
2
~ dY
= Ey Y

2m dy 2
~2 dZ 2
= Ez Z

2m dz 2

(400)

(411)

of k-space, where V = lx ly lz is the volume of

the object itself. Suppose the sample contains N
atoms , and each contribute q electrons. They
will fill up one octant of a sphere in k-space,
whose radius ,kF is determined by the fact that
each pair of electrons require a volume 3 /V

(401)
(402)

and E = Ex + Ey + Ez . Letting

1
8

2mEy
2mEx
2mEz
kx
, ky
, kz
~
~
~
(403)
we obtain the general solutions

4 3
k
3 F

Nq
=
2

3
V

(412)

thus
kF = (3 2 )1/3

(413)

where
X(x) = Ax sin(kx x) + Bx cos(kx x)

(404)

Y (y) = Ay sin(ky y) + Bx cos(ky y)

(405)

Z(z) = Az sin(kz z) + Bx cos(kz z)

(406)

(414)

is the free electron density ( the number of

free electrons per unti volume)
The boundery seperating occupied and unoccupied states, in k-space, is called the Fermi
surface. The corresponding energy is called the
Fermi energy, EF ; for a free electron gas,

The boundery conditions require X(0) =

Y (0) = Z(0) = 0, so Bx = By = B + z = 0,
and X(lx ) = Y (ly ) = Z(lz ) = 0, so that

kx lx = nx , ky ly = ny , kz lz = nz

Nq
V

(407)

~2
(3 2 )2/3
(415)
2m
The total energy of the electron gas can be
calculated as follows; Each of these states carries
an energy ~2 k 2 /2m, so the energy of the shell is
EF =

where each n is a positive integer

nx = 1, 2, 3, .., ny = 1, 2, 3, .., nz = 1, 2, 3, ..
(408)
The normalized wave functions are
s

~2 k 2 V 2
k dk
2m 2
and hence the total energy is
dE =






nx
ny
nz
x sin
y sin
z
Z kF
lx
ly
lz
~2 V
~2 kF5 V
4
Etot =
k
dk
=
(409)
2m 2 0
10 2 m
and the allowed energies are
~2 (3 2 N q)5/3 2/3
V
(417)
=
10 2 m


~2 k 2
n2x
n2x
~2 2 n2x
This quantum mechanical energy plays a role
=
+
+
Enx ny nz =
2m
lx2
lx2
lx2
2m
rather analogous to the internal thermal energy
(410)
(U ) of an ordinary gas. In particular, it exerts a
where k is the magnitude of the wave vector,
pressure on the walls, for if the box expands by
k (kx , ky , kz ).
an amount dV , the total energy decreases
If you imagine a three-dimensional space,
with axes kx , ky , kz , and planes drawn in at kx =
2 ~2 (3 2 N q)5/3 5/3
(/lx ), (2/lx ), (3/lx ), ..., at ky = (/ly ), (2/ly ), (3/ly ), ...,
V
dV
dEtot =
3
10 2 m
and at kz = (/lz ), (2/lz ), (3/lz ), .... Each
2
dV
block in this grid, and hence each state, occu= Etot
(418)
pies a volume
3
V
nx ny nz =

8
sin
lx ly lz

(416)

24

and this shows up as work done on the outside (dW = P dV ) by the quantum pressure P .
Evidently
2 ~2 kF5
(3 2 )2/3 ~2 5/3
2 Etot
=
=

2
3 V
3 10 m
5m
(419)
this is sometimes called degeneracy pressure strictly due to quantum effects.
P =

25