Angular Momentum

Chapter 2
Angular Momentum, Hydrogen

Atom, and Helium Atom
Contents
2.1 Angular momenta and their addition . . . . . . . . . . . . . . . . . . 24
2.2 Hydrogenlike atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3 Pauli principle, Hunds rules, and periodical table . . . . . 42
2.4 Ground state of helium atom: 1st approximation . . . . . . 48
Basic Questions
A. What are the eigenvalues of angular momentum operator?
B. What are the quantum numbers of a state of the single
electron in hydrogen atom?
C. What is total electron spin of ground-state helium atom,
and the spin eigenstate?
23
24CHAPTER 2. ANGULAR MOMENTUM, HYDROGENATOM, AND HELIUMATOM
2.1 Angular momentum and addition of two an-
gular momenta
2.1.1 Schr odinger Equation in 3D
Consider the Hamiltonian of a particle of mass m in a central potential V (r)
H =
h
2
2m
2
+V (r) .
Since V (r) depends on r only, it is natural to express
2
in terms of spherical
coordinates (r, , ) as
2
=
1
r
2
r
_
r
2

r
_
+
1
r
2
sin
_
sin

_
+
1
r
2
sin
2
2
.
Operators in Spherical Coordinates
A. Laplacian operator
By coordinate transformation between Cartesian (x, y, z) and spherical coordi-
nates (r, , )
x = r sin cos , r =
_
x
2
+y
2
+z
2
y = r sin sin , tan
2
=
x
2
+y
2
z
2
z = r cos , tan =
y
x
we have
r
x
= sin cos ,
r
y
= sin sin ,
r
z
= cos
x
=
1
r
cos cos ,

y
=
1
r
cos sin ,

z
=
1
r
sin
x
=
1
r
sin
sin
,

y
=
1
r
cos
sin
,

z
= 0 .
Using the derivative rule
x
=
r
x
r
+

x
+

x
2.1. ANGULAR MOMENTUMAND ADDITIONOF TWOANGULAR MOMENTA25

= sin cos

r
+
1
r
cos cos

1
r
sin
sin
y
= sin sin

r
+
1
r
cos sin

1
r
cos
sin
z
= cos

r

1
r
sin

Therefore
2
x
2
+

2
y
2
+

2
z
2
=
_
sin cos

r
+
1
r
cos cos

1
r
sin
sin
_
sin cos

r
+
1
r
cos cos

1
r
sin
sin
_
+
_
sin sin

r
+
1
r
cos sin

1
r
cos
sin
_
sin sin

r
+
1
r
cos sin

1
r
cos
sin
_
+
_
cos

r

1
r
sin

_
cos

r

1
r
sin

_
and this is equal to, after some considerable algebra
2
=

2
r
2
+
1
r
2
2
+
1
r
2
sin
2
2
+
2
r
r
+
cot
r
2
=
1
r
2
r
_
r
2

r
_
+
1
r
2
sin
_
sin

_
+
1
r
2
sin
2
2
=
1
r
2
r
_
r
2

r
_
+
1
r
2
A(, )
with denition
A(, )
1
sin
_
sin

_
+
1
sin
2
2
.
B. Angular momentum operators
Consider rst the z-component, using the above formulas for

x
and

y
L
z
= i h
_
x

y
y

x
_
= (i h) r sin cos
_
sin sin

r
+
1
r
cos sin

1
r
cos
sin
_
(i h) r sin sin
_
sin cos

r
+
1
r
cos cos

1
r
sin
sin
_
= i h

similarly we can derive the x- and y-components as
L
x
= i h
_
sin

cot cos

L
y
= i h
_
+cos

cot sin

_
.
From the denition of the raising and lowering operators

L
x
i
L
y
it is straightforward to obtain
= i he
i
_
i

cot

_
.
C. Angular momentum square
In order to obtain the square of angular momentum operator in the spherical
coordinates, consider
_
L
x
_
2
_
L
x
_
2
h
2
=
_
sin

+ cot cos

_
2
= sin

sin

+ sin

cot cos

+ cot cos

sin

+cot cos

cot cos

= sin
2
2
+ sin cos

cot

+ cot cos
2
+cot cos sin

2
cot
2
cos sin

+ cot
2
cos
2
2
_
L
y
_
2
h
2
=
_
cos

cot sin

_
2
= cos
2
2
sin cos

cot

+ cot sin
2
cot cos sin

2
+ cot
2
sin cos

+ cot
2
sin
2
2
now
L
2
h
2
=
L
2
x
+

L
2
y
+

L
2
z
h
2
=

2
2
+ cot

+
_
cot
2
+ 1
_

2
2
=
1
sin
sin

+
1
sin
2
2
=

A(, )
=
1
sin
sin

1
sin
2
L
2
z
h
2
where

A(, ) is as dened before in the Laplacian
2
.
The Schr odinger eq. becomes
_
h
2
2m
_
1
r
2
r
_
r
2

r
_
+
1
r
2
sin
_
sin

_
+
1
r
2
sin
2
2
_
+V (r)
_
(r, , )
= E(r, , )
or
__
h
2
2m
1
r
2
r
_
r
2

r
_
+V (r)
_
+
L
2
2mr
2
_
(r, , ) = E(r, , ) .
This eq. is separable. Let
(r, , ) = R(r) Y (, )
where Y (, ) is assumed to be the eigenstate of

L
2
with eigenvalue
L
2
Y (, ) = Y (, )
we have the equation for the radial part of wavefunction
__
h
2
2m
1
r
2
r
_
r
2

r
_
+V (r)
_
+

2mr
2
_
R(r) = ER(r) .
The solution of this equation depends on the given potential V (r). But the solution
for the angular part of wavefunction Y (, ) is universal and can be discussed in
general.
2.1.2 Operators and their algebra
Classically, angular momentum is dened as
L = r p
or in component form
L
x
= yp
z
zp
y
, L
y
= zp
x
xp
z
, L
z
= xp
y
yp
x
in QM, they all become operator
L
x
= y p
z
z p
y
,

L
y
= z p
x
x p
z
,

L
z
= x p
y
y p
x
.
Their commutation relations are given by
_
L
x
,

L
y
_
= [ y p
z
z p
y
, z p
x
x p
z
]
= [ y p
z
, z p
x
] + [ z p
y
, x p
z
]
= y [ p
z
, z] p
x
+ [ z, p
z
] p
y
x
= i h y p
x
+i h p
y
x
= i h
L
z
_
L
y
,

L
z
_
= i h
L
x
_
L
z
,

L
x
_
= i h
L
y
we can memorize these relations by
L = i h
L .
In spherical coordinates, these operators are expressed as
L
x
= i h
_
sin

cot cos

L
y
= i h
_
+cos

cot sin

L
z
= i h

and
L
2
= h
2
_
1
sin
sin

+
1
sin
2
2
_
.
Hence the Laplacian operator
2
and Hamiltonian take the following simple form
2
=
1
r
2
r
r
2

r

L
2
h
2
r
2
H =
h
2
2m
1
r
2
r
r
2

r
+V (r) +
1
2m
L
2
r
2
It is easy to see

L
z
commutes with

L
2
_
L
z
,

L
2
_
= 0
and

L
2
commute with operators

H ,
_
L
2
,

H
_
= 0 .
(note: we also have
_
L
x
,

L
2
_
=
_
L
y
,

L
2
_
= 0) Therefore we can nd a wavefunction
which is eigenfunctions to both

H,

L
2
, and

L
z
. Furthermore, since they are separable,
the eigenfunction of

H can be written in general as
n.l,m
(r, , ) = R
nl
(r)
l
()
m
() = R
nl
(r) Y
l,m
(, )
with
L
z
m
() =
m
m
() i

m
() =
m
m
()
L
2
Y
l,m
(, ) =
l,m
Y
l,m
(, )
_
h
2
sin
sin

+

2
m
sin
2
l
() =
l,m
l
()
H
n.l,m
(r, , ) =
n,l,m
n.l,m
(r, , )
h
2
2
1
r
2
r
r
2

r
+V (r) +
1
2
l,m
r
2
_
R
nl
(r) =
n,l,m
R
nl
(r)
In Dirac notation
m
() |m
Y
l,m
(, ) |l, m
n.l,m
(r, , ) |n, l, m .
Instead of dealing with

L
x
,

L
y
, and

L
z
, one can dene angular raising and lowering
operators

L
+
and

L
as,

L
x
i
L
y
= i he
i
_
i

cot

_
and we have the equivalent set

L
x
,

L
y
, and

L
z
or

L
,

L
+
and

L
z
. The algebra for
this 2nd set is more convenient. It is easy to show the commutations between three
operators L
z
, L
are given by
_
L
z
,

L
_
= h
,
_
L
+
,

L
_
= 2 h
L
z
.
Note: Compare this algebra with harmonic oscillator
_
a, a
_
= 1. These algebra will
determine the eigenfunctions and eigenvalues of

L
2
. It is also easy to derive
L
+
=

L
2

L
2
z
+ h
L
z
,
L
+
=

L
2

L
2
z
h
L
z
,
and
L
2
=

L
2
z
+ h
L
z
+

L
L
+
=

L
2
z
h
L
z
+

L
+
=

L
2
z
+
1
2
_
L
+
+

L
L
+
_
.
Note: compare this with harmonic oscillator

H = h
_
a
a +
1
2
_
.
2.1.3 Eigenvalues and eigenfunctions
(i) Solution for
m
() is simple
i h

m
() =
m
m
()
m
() =
1
2
e
im/ h
and using spherical symmetry of the system, we must have
m
( + 2) =
m
()

m
h
= m = 0, 1, 2,
therefore
L
z
|m = m h |m , m = 0, 1, 2, .
(ii) Consider the eigenequations
L
2
|l, m =
l,m
|l, m
it is obvious |l, m is also eigenfunction of

L
z
L
z
|l, m = hm|l, m
we next examine the eect of

L
+
and

L
when acting on |l, m. We divide the whole

process by following steps.
(a) Using the commutation relationship
_
L
z
,

L
_
= h
, we have
L
z
|l, m =
_
L
z
_
|l, m =
_
hm
_
|l, m = h(m1)

L
|l, m
therefore,

L
+
eectively increases m by a unity and

L
eectively decreases m by a
unity, hence we write
|l, m = C
(l, m) |l, m1
where C
(l, m) are constants. Therefore, the states |l, m with m = 0, 1, 2,

can be related by raising or lowering operator

L
.
(b)

L
2
degeneracy. The eigenvalue of

L
2
is independent of m,
l,m
=
l
L
2
|l, m =
l
|l, m .
Proof: using
_
L
2
,

L
_
= 0, we have
L
2
|l, m = C
L
2
|l, m1 =
l,m1
C
|l, m1 =
l,m1
|l, m
=

L
L
2
|l, m =
l,m
|l, m
hence
l,m1
=
l,m

l .
(c) For a given
l
(or l), the values of m must be bounded. Because
__
L
2
x
+

L
2
y
__
>
0,

L
2
=

L
2
x
+

L
2
y
+

L
2
z

L
2
x
+

L
2
y
+ h
2
m
2
. Let this maximum value of |m| be M
l
l,
remember l is only an index for labeling. Hence
|l, m , m = 0, 1, 2, , l .
Altogether, there are (2l + 1) values of m.
(d) Consider state |l, l. Since its m is at maximum, cannot increase any more,
we must have
L
+
|l, l = 0
hence
L
2
|l, l =
_
L
2
z
+ h
L
z
+

L
L
+
_
|l, l = h
2
_
l
2
+l
_
|l, l
= h
2
l (l + 1) |l, l .
Using the degeneracy of

L
2
, we have
L
2
|l, m = h
2
l (l + 1) |l, m , m = 0, 1, 2, , l .
(e) We can now determine the coecients C
(l, m)
|l, m = C
(l, m) |l, m1 .
Using the fact that
_
=

L
+
, assuming |l, m and |l, m1 have already been
normalized, we have
L
+
|l, m = C
+
(l, m) |l, m+ 1
C
2
+
(l, m) =
_
l, m|
_ _
L
+
|l, m
_
= l, m|
L
+
|l, m
= l, m|
_
L
2

L
2
z
h
L
z
_
|l, m = h
2
[l (l + 1) m(m+ 1)]
or
C
+
(l, m) = h
_
l (l + 1) m(m+ 1)
similarly
C
(l, m) = h
_
l (l + 1) m(m1) .
(f) From the denition of

L
+
in spherical coordinate
L
+
= i he
i
_
i

cot

_
and using the fact that
L
+
|l, l = 0
we derive the equation for the highest-order spherical harmonic function, |l, l =
Y
ll
(, )
_

l cot
_
Y
ll
= 0, Y
ll
= c e
il
sin
l
, c =
(1)
l
_
(2l + 1)!!
(2l)!!
where c is the normalization constant, determined by
2
_

0
sin
2l+1
d = 2
_
_
/2
0
+
_

/2
_
sin
2l+1
d = 2
_
_
/2
0
sin
2l+1
d +
_
/2
0
cos
2l+1
d
_
= 4
_
/2
0
sin
2l+1
d = 4
(2l)!!
(2l + 1)!!
.
By applying L
repeatedly, we obtain the general spherical harmonic, Y

lm
(, ).
(iii) For a general angular momentum

L, all above derivations are still valid,
except that we do not have the representation

L
z
= i h/, etc. And the corre-
sponding rotational invariance ( + 2) = () m = 0, 1, 2, are hence
not necessarily true. Hence we derive the following general angular momentum
theorem,
L
2
|l, m = h
2
l (l + 1) |l, m
L
z
|l, m = hm|l, m
m = l, l + 1, , l 1, l
with (2l + 1) values of m. As 2l + 1 must be an integer, l must be an integer or
half-odd-integer.
Example: Electron spin. An electron has an intrinsic angular momentum,
called spin, denoted as

S, with quantum number S. Experimentally, it was found
S = 1/2. The corresponding z-component quantum number is therefore given by
m = 1/2, 1/2. Therefore, applying the above universal algebra to the spin angular
momentum, we have
S
2
|S, m = h
2
S (S + 1) |S, m
= h
2
1
2
_
1
2
+ 1
_
|S, m
=
3
4
h
2
|S, m , m =
1
2
,
1
2
S
z
|S, m = hm|S, m .
Since for an electron, S = 1/2 is xed and well-know,

S
2
=
3
4
h
2
is a constant. We
denote m =
1
2
as spin-up state, and m =
1
2
as spin-down state, we write
S, m =
1
2
_
= |
S, m =
1
2
_
= |
and
S
z
| =
h
2
| ,

S
z
| =
h
2
| .
2.1.4 Addition of Angular Momenta
We know that the eigenstates of a general angular momentum

L has two quantum
numbers (qn): l - angular momentum qn and m - magnetic qn, the corresponding
eigen eqs. are
L
2
|l, m = h
2
l (l + 1) |l, m
L
z
|l, m = hm|l, m , m = l, l + 1, , l 1, l .
The reason is simply that these two operators commute with one another
_
L
2
,

L
z
_
=
0. People usually refer these proper qns as good quantum numbers.
Now we consider addition of two angular momenta
L =

L
1
+

L
2
L
2
=

L
2
1
+

L
2
2
+ 2
L
1
L
2
L
1
L
2
=

L
x1
L
x2
+

L
y1
L
y2
+

L
z1
L
z2
.
Physical examples are the total angular momentum of two separate particles, or the
total momentum of the orbital and spin angular momenta of a single particle, etc.
The eigen states of

L
2
1
and

L
2
2
are known separately as
L
2
i
|l
i
, m
i
= h
2
l
i
(l
i
+ 1) |l
i
, m
i
, i = 1, 2
L
zi
|l
i
, m
i
= hm
i
|l
i
, m
i
, m
i
= l
i
, l
i
+ 1, , l
i
1, l
i
.
We want to know what are the good qns for the eigenstates of total

L, and what are
the eigenvalues.
The algebra for total

L is the same as before. It is easy to prove
_
L
2
,

L
2
1
_
=
_
L
2
,

L
2
2
_
=
_
L
2
,

L
z
_
= 0
L
z
=

L
z1
+

L
z2
but
_
L
2
,

L
z1
_
= 2
_
L
x1
L
x2
+

L
y1
L
y2
,

L
z1
_
= 2i h
_
L
y1
L
x2
+

L
x1
L
y2
_
= 0
_
L
2
,

L
z2
_
= 2
_
L
x1
L
x2
+

L
y1
L
y2
,

L
z2
_
= 2i h
_
L
x1
L
y2
+

L
y1
L
x2
_
= 0 .
Therefore, we can nd a common eigen state to

L
2
1
,

L
2
2
,

L
2
,

L
z
and denote as |l
1
, l
2
, l, m,
these are good quantum numbers. (m
1
and m
2
are not good quantum numbers).
The eigen eqs. are
L
2
1
|l
1
, l
2
, l, m = h
2
l
1
(l
1
+ 1) |l
1
, l
2
, l, m
L
2
1
|l
1
, l
2
, l, m = h
2
l
2
(l
2
+ 1) |l
1
, l
2
, l, m
L
2
|l
1
, l
2
, l, m = h
2
l (l + 1) |l
1
, l
2
, l, m
L
z
|l
1
, l
2
, l, m = hm|l
1
, l
2
, l, m , m = l, l + 1, , l 1, l
etc.
The question is: for a given l
1
and l
2
, what are the possible values for l. For this
purpose, we consider the following few steps:
(a) Total dimensionality (no. of independent states) is (2l
1
+ 1) (2l
2
+ 1). This
will restrict the number of possible l
l
(2l + 1) = (2l
1
+ 1) (2l
2
+ 1) .
(b) Starting with the state
|l
1
, m
1
= l
1
|l
2
, m
2
= l
2
it is eigenstate of

L
z
L
z
(|l
1
, m
1
= l
1
|l
2
, m
2
= l
2
) = h (l
1
+l
1
) (|l
1
, m
1
= l
1
|l
2
, m
2
= l
2
)
and since m = l
1
+ l
1
is the largest possible value for m, l = l
1
+ l
1
is the largest
possible value for l. This is the only one. Hence
|l
1
, l
2
, l
1
+l
1
, l
1
+l
1
= |l
1
, l
1
|l
2
, l
2
(c) Next, consider state with m = l

1
+ l
1
1. There are two possible l, with
l = l
1
+l
1
and l = l
1
+l
1
1, hence denoted as
|l
1
, l
2
, l
1
+l
1
, l
1
+l
1
1 , |l
1
, l
2
, l
1
+l
1
1, m = l
1
+l
1
1
In terms of |l
1
, m
1
|l
2
, m
2
representation, these are a linear combination of two pos-
sible states, as seen in the following table
m
1
m
2
m
l
1
l
2
l
1
+l
2
l
1
l
2
1 l
1
+l
2
1
l
1
1 l
2
l
1
+l
2
1
l
1
l
2
2 l
1
+l
2
2
l
1
1 l
2
1 l
1
+l
2
2
l
1
2 l
2
l
1
+l
2
2

(d) Continue this process, the possible value of l decreases by one, and number of
states increases by one. Therefore,
l = l
1
+l
2
, l
1
+l
2
1, l
1
+l
2
2, , |l
1
l
2
|
the minimum value is |l
1
l
2
| since l must be a positive number.
(e) And we have identity
l
1
+l
2
l=|l
1
l
2
|
(2l + 1) = (2l
1
+ 1) (2l
2
+ 1)
= 2 (l
1
l
2
+ 0) + 1, let l
1
> l
2
+2 (l
1
l
2
+ 1) + 1
+2 (l
1
l
2
+ 2) + 1

+2 (l
1
l
2
+ 2l
2
) + 1
= 2l
1
(2l
2
+ 1) 2l
2
(2l
2
+ 1) + 2
1
2
2l
2
(2l
2
+ 1) + (2l
2
+ 1)
= (2l
1
+ 1) (2l
2
+ 1)
where we have used
1 + 2 + 3 + +n =
1
2
n(n + 1) .
Angular momentum addition theorem: Total angular momentum

L =

L
1
+

L
2
eigenstates are denoted by good quantum numbers |l
1
, l
2
, l, m, and eigenvalues are
given by
L
2
|l
1
, l
2
, l, m = h
2
l(l + 1)|l
1
, l
2
, l, m,

L
z
|l
1
, l
2
, l, m = hm|l
1
, l
2
, l, m
with m = l, l + 1, ..., l 1, l, and l = l
1
+l
2
, l
1
+l
2
1, ..., |l
1
l
2
|.
Example. An electron is in a state with orbital angular momentum l = 5. Its
total angular momentum
J =

L +

S
has possible quantum numbers as
J =
11
2
,
9
2
and the total number of states
_
2
11
2
+ 1
_
+
_
2
9
2
+ 1
_
= (2 5 + 1)
_
2
1
2
+ 1
_
= 22 .
Example. Eigenvalues of operator

H =

L
S. Write this operator as
H =

L
S =
1
2
_
J
2
L
2
S
2
_
and its eigenstates are characterized by the good quantum numbers |l, s, j, m
j
. So
H|l, s, j, m
j
=
1
2
_
J
2
L
2
S
2
_
|l, s, j, m
j
=
h
2
2
[j (j + 1) l (l + 1) s (s + 1)] |l, s, j, m
j
=
h
2
2
_
j (j + 1) l (l + 1)
3
4
_
|l, s, j, m
j
, j = l
1
2
.
Two spin-1/2 systems. Two interacting spins have the following Heisenberg
Hamiltonian
H =
S
1
S
2
where is the coupling constant. Determines its eigenvalues and eigenstates. Write
the Hamiltonian as
H =
S
1
S
2
=

2
_
S
2
S
2
1
S
2
2
_
,

S =

S
1
+
S
2
hence its eigenvalues are, using s
1
= s
2
= 1/2
E
s
=
h
2
2
[s (s + 1) s
1
(s
1
+ 1) s
2
(s
2
+ 1)]
=
h
2
2
_
s (s + 1)
3
2
_
.
By the angular momentum addition theorem, there are only two possible values for
s: 0, 1. So the eigenvalues are
E
0
=
3 h
2
4
, E
1
=
h
2
4
.
In order to determine the corresponding eigenstates |s, m, we rst observe that,
considering the quantum number m for

S
z
, there is only one state for E
0
with m = 0,
denoted as |0, 0 with eigenequation
H|0, 0 = E
0
|0, 0 ;
there are three states for E
1
since there three possible m values m = 0, 1, denoted
as |1, 0 and |1, 1 with eigen equations
H|1, 0 = E
1
|1, 0 ,

H|1, 1 = E
1
|1, 1 .
Note that these later three states are degenerate. All these four states are obtained
from the following four basis states |
1
|
2
, |
1
|
2
, |
1
|
2
, |
1
|
2
. It is easy to
see that only one basis state |
1
|
2
gives m = 1, hence
|1, +1 = |
1
|
2
;
similarly there is only one state with m = 1, hence
|1, 1 = |
1
|
2
;
and the other two basis state, |
1
|
2
and |
1
|
2
, clearly have m = 0. Their com-
binations will give |0, 0 and |1, 0. The only two possible independent combinations
are
1
2
(|
1
|
2
|
1
|
2
)
with the normalization factor 1/
2. By directly applying the Hamiltonian

H to these
two states (see Exercise 2, Question 4), it is easy to show that
|0, 0 =
1
2
(|
1
|
2
|
1
|
2
)
and
|1, 0 =
1
2
(|
1
|
2
+|
1
|
2
) .
Conclusion: the two-spin Hamiltonian

H =
S
1
S
2
has two levels, a singlet level with
energy E
0
=
3 h
2
4
and state
1
2
(|
1
|
2
|
1
|
2
) and a triplet level with energy
E
1
=
h
2
4
and three states |
1
|
2
,
1
2
(|
1
|
2
+|
1
|
2
) and |
1
|
2
.
2.2 Hydrogen-like Atom
The system of a Hydrogen-like atom consists of an electron and a nucleus containing
Z protons, interacting with attractive Coulomb potential. The Hamiltonian for the
relative motion is given by
H =
h
2
2
2
+V (r) , V (r) =
e
2
4
0
Z
r
=
h
2
2
1
r
2
r
r
2

r
+V (r) +
1
2
L
2
r
2
with reduced mass = m
e
m
n
/(m
e
+ m
n
) where m
n
is the nuclear mass. The
Schr odinger eq.
H|n, l, m =
n,l,m
|n, l, m ,

H
n,l,m
(r, , ) =
n,l,m
n,l,m
(r, , )
with
n,l,m
(r, , ) = R
n,l,m
(r) Y
l,m
(, ) |n, l, m
Y
l,m
(l, m) =
l,m
()
m
() |l, m
m
() |m , m = 0, 1, 2, , l
2.2. HYDROGEN-LIKE ATOM 39
and
L
2
|l, m = h
2
l (l + 1) |l, m ,

L
z
|l, m = hm|l, m
Therefore, eigen problem for

H becomes, R
n,l,m
(r) R
n,l
(r) ,
n,l,m
n,l
_
h
2
2
1
r
2
r
r
2

r
+V (r) +
h
2
l (l + 1)
2
1
r
2
_
R
n,l
(r) =
n,l
R
n,l
(r)
Solution of this eigenequation is not universal, depending on the given V (r). For the
Coulomb potential V (r) =
e
2
4
0
1
r
, we have
l = 0, 1, 2, , (n 1)
for the condition existing solution,
n,l
=
n
=
e
2
8
0
a
0
Z
2
n
2
13.6
1
n
2
(eV) , a
0
=
4
0
h
2
e
2
0.53 10
10
(m)
for the eigenvalues, and
R
n,l
(r) = e
Zr/na
0
r
l
_
C
0
+C
1
r +C
2
r
2
+ +C
nl1
r
nl1
_
for the eigenfunctions, where C
i
are real constants. We plot the rst few radial
probability distributions in Fig. 2. In Fig. 3, we plot the angular parts probability
distributions. (Figures are copied from Gasiorowiczs Quantum Physics)
Fig. 2 Radial probability distributions r
2
R
2
nl
(r). The horizontal axis
is r in units of a
0
.
Fig. 3 Angular probability distributions |Y
lm
(, )|
2
. The sketches rep-
resent sections of the distributions made in the z-x plane. It should be
understood that the three-dimensional distributions are obtained by ro-
tating the gures about the z-axis.
2.2. HYDROGEN-LIKE ATOM 41
Summary of Hydrogen Atom QM
QM of Hydrogen (or Hydrogen-like atoms)
H|n, l, m, m
s
= E
n
|n, l, m, m
s
, E
n
= 13.6
Z
2
n
2
(eV) ,
|n, l, m, m
s
R
n,l
(r) Y
l,m
(, )
ms
H =
h
2
2
1
r
2
r
r
2

r

Ze
2
4
0
1
r
+
1
2
L
2
r
2
with reduced mass and electron spin m
s
= 1/2. The degeneracy for each given n
is
D
n
=
n1
l=0
(2l + 1) = n
2
.
Y
l,m
(, ) is the eigenstate of angular momentum

L
2
L
2
|l, m = h
2
l (l + 1) |l, m , |l, m Y
l,m
(, ) =
l,m
()
m
()
L
2
= h
2
_
1
sin
sin

1
sin
2
L
2
z
h
2
_
with degeneracy for each given l
l
m=l
1 = 2l + 1
where
m
() is the eigenstate of

L
z
L
z
|m = hm|m , |m
m
() , m = 0, 1, 2, , l
L
z
= i h

,
m
() =
1
2
e
im
.
2.3 Pauli exclusion principle and periodic table
In this section, we introduce some important concepts of quantum many-body theory
as atoms and molecules are many-body systems. We will mainly ignore the inter-
actions between electrons and only consider their Coulomb repulsion by empirical
rules.
Consider two identical particle system (e.g., two electrons in a Helium atom).
Suppose their wavefunction is (x
1
, x
2
) , where x
i
is the coordinate of the ith particle,
e.g., x = (r, ) with r the spatial position and =, the spin of the particle, etc.
Consider the exchange operation

P : exchanging the coordinates of the two par-
ticles,
P
12
(x
1
, x
2
) = (x
2
, x
1
) .
If we choose (x
1
, x
2
) as an eigenstate of

P
12
with eigenvalue p, then the eigenequa-
tion is
P
12
(x
1
, x
2
) = p (x
1
, x
2
) .
Acting

P
12
second time we get back to the original state,
p
2
(x
1
, x
2
) = (x
1
, x
2
) , or p
2
= 1
Therefore, p can only has two values
p = 1.
The quantum particles with p = 1 are referred to as Boson particles, or simply
Bosons; The quantum particles with p = 1 are referred to as Fermion particles, or
simply Fermions. A more general analysis shows that with integer spin are always
Bosons, and particles with half-odd-integer spins are always Fermions. For example,
electrons and protons are Fermions, and photons (light quanta) are Bosons; Helium-4
is Boson because its spin is zero, but Helium-3 atom is Fermion with spin 1/2.
For a general quantum many-body wavefunction, the exchange operation is
P
nm
( , x
n
, , x
m
, ) = ( , x
m
, , x
n
, ) ,
where + corresponds to Boson system, and to Fermion system. This is a exact
property of a quantum many-body system.
Now let us consider its consequence. A general Hamiltonian of N-particle system
is
H =
N
i=1
H
i
+

V
2.3. PAULI EXCLUSION PRINCIPLE AND PERIODIC TABLE 43
where

V is the interaction potential and usually given by
V =
1
2
N
i=j
V (r
ij
) .
For example
V =
e
2
4
0
1
r
12
for helium atom and
V =
e
2
4
0
_
1
r
12
+
1
r
13
+
1
r
23
_
for lithium. Now consider the simplest approximation by ignoring

V , (the corre-
sponding wavefunction is the zero-order approximation to the true eigenstate), the
Hamiltonian becomes separate
H
N
i=1
H
i
and the wavefunction becomes a product of single particle states. In general, we
refer to such approximation as the independent-particle approximation. The
essence of this approximation is to keep the quantum nature of particles but ignoring
their dynamic interactions (later, we will include some corrections due to Coulomb
repulsion by empirical Hunds rule). Assume that we have solved the single-particle
Schr odinger eq.
H
1
k
(x
1
) = E
k
k
(x
1
)
the total wavefunction may be written as
(x
1
, x
2
, , x
N
)
k1
(x
1
)
k2
(x
2
)
kN
(x
N
)
not taking the exchange symmetry into account. In order to include this important
quantum symmetry, consider rst a 2-particle system, N = 2,
B
(x
1
, x
2
) =
1
2
[
n
1
(x
1
)
n
2
(x
2
) +
n
1
(x
2
)
n
2
(x
1
)] for Bosons
[or
n1
(x
1
)
n1
(x
2
) etc.] and
F
(x
1
, x
2
) =
1
2
[
n
1
(x
1
)
n
2
(x
2
)
n
1
(x
2
)
n
2
(x
1
)] for Fermions
so that
B
(x
1
, x
2
) =
B
(x
2
, x
1
) for Bosons and
F
(x
1
, x
2
) =
F
(x
2
, x
1
) for
Fermions. One can also construct a symmetric wavefunction for two Bosons by a
single wavefunction as
B
(x
1
, x
2
) =
n
1
(x
1
)
n
1
(x
2
), or
n
2
(x
1
)
n
2
(x
2
).
Extending t o N-particle system, for the Fermions, we can write the wavefunction
as a determinant, Slater determinant,
(x
1
, , x
N
) =
1
N!
n
1
(x
1
)
n
1
(x
2
)
n
1
(x
N
)
n
2
(x
1
)
n
2
(x
2
)
n
2
(x
N
)

n
N
(x
1
)
n
N
(x
2
)
n
N
(x
N
)
.
Notice that if k
1
= k
2
,
F
(x
1
, x
2
) = 0, but not
B
(x
1
, x
2
). This indicates that two
Fermions cannot occupy the same state, but it two bosons are allowed to occupy the
same state. It can be extended to a more general statement:
A state can only be occupied by at most a single Fermion;
But it can be occupied by any number of Bosons.
The rst above statement is Pauli exclusion principle. The second statement is
the property that leads to the so-called Bose-Einstein condensation of bosons at low
temperature. As active ingredients in atoms and molecules are electrons which are
fermions, we will mainly use Pauli principle. It is obvious that in the independent-
particle approximation (e.g., ignoring particle interactions), the ground state of an
N-electron system is given by the Slater determinant constructed from the lowest
N single particle states. For atoms, these single particles states are naturally the
eigenstates of hydrogenlike atoms as we discussed previously. For molecules, these
single particle states are constructed by a linear combinations of atomic states at
dierent nuclear congurations. We will discuss QM of molecules in the last chapter.
Sometimes it is convenient to separate total wavefunction as discussed above into
product of spatial and spin parts of wavefunctions, namely
(x
1
, , x
N
) = (r
1
, , r
N
)(
1
, ,
N
).
Hence, if spin wavefunction is antisymmetric, the spatial wavefucntion must be
symmetric in order for the total wavefunction to be antisymmetric, vice versa.
Now we apply this simple analysis to atoms, the elements on the periodical table,
where the identical fermions are electrons with spin-1/2. We will qualitatively discuss
the ground states of the atoms. In the next section, we will attempt to calculate the
ground-state energy value of the two electron system, helium atom. By solving the
Schr odinger equation of hydrogenlike atoms in the previous section, we know the elec-
trons states in an atom can be characterized by four quantum numbers (n, l, m, m
s
):
n - principle quantum number specied main energy levels (shells), l - (orbital) angu-
lar momentum quantum number, and m - (orbital) magnetic quantum number and
m
s
- spin magnetic quantum number. We extend this to many-electrons state ig-
noring the interactions, spin-orbit couplings, etc., by using the independent-particle
approximation. Using notation
l = 0 s state, 1 p state, 2 d state
and noticing m and m
s
are degenerate quantum numbers, we conclude that s shell
can take up to two electrons (single orbital with m = 0 but one electron with spin up
m
s
= 1/2, the other electron with spin down m
s
= 1/2); p shell can take up to 6
electrons (three states specied by m = 1, 0, 1, each can take one electron with spin
up and one electron with spin down); d shell can take up to 10 electrons (5 states
with m = 2, 1, 0, 1, 2, each can take two electrons), etc. These energy levels are
ordered as,
orbitals (shells) : 1s 2s 2p 3s 3p 4s 3d 4p 5s
electron no. : 2 4 10 12 18 20 30 36 38
In the above table, we also list total possible maximal number of electrons.
In this independent-particle picture, the way each electron of an atom occupies
a particular hydrogen state is called electron conguration. As we are mainly in-
terested in the ground state, the electron conguration of an atom is given by lling
these hydrogen orbitals from the lowest, in the ordered series as
(1s)(2s)(2p)(3s)(3p)(4s)(3d)(4p)(5s) .
We notice that a given electron conguration will not uniquely determine some basic
properties (such as total angular momentum, spins etc.) of the corresponding atom.
More information can be specied by using the so called atomic spectral term (or
atomic term) to represent states of an atoms. Some correction to independent-particle
approximation for the ground-state atomic term due to Coulomb repulsion will be
considered by the empirical rules.
Atomic spectral terms. We use notation
(2S+1)
L
J
to denote a particular atomic
state where S is its total spin, L its total orbital angular momentum and J the total
angular momentum (spins and orbitals). We use capital Latin letters for each value
of orbital quantum number as
L = 0 1 2 3 4 5 6 7 8 9 10
S P D F G H I K L M N
For example,
2
P
3/2
denotes levels with L = 1, S = 1/2 and J = 3/2. The dierence
in energy between atomic levels having dierent L and S but the same electron
conguration is due repulsive Coulomb interaction between electrons. These energy
dierences are small. We have the following empirical Hunds rules (F.Hund, 1925)
concerning relative position of levels with the same conguration but dierent L and
S:
(i) For a given shell (conguration), the term with greatest possible value of S gives
the lowest energy;
(ii) The greatest possible value of L (for this S) has the lowest energy;
(iii) For half or less than half lling shell, J = |LS| gives lowest energy; For more
than half-lling shell, J = L +S gives lowest energy.
The origin of the rst rule is obvious: the largest total spin corresponds to symmetric
(parallel) spin wavefunction and antisymmetric orbital wavefunction, the later reduces
electron-electron repulsive interaction energy.
Example. Helium (Z = 2) has a simple conguration (1s)
2
. Hence S = 0 and
L = 0. The ground state term is
1
S
0
with J = 0. We will use this term to construct
an approximate wavefunction to calculate its ground-state energy in the next section.
Example. Carbon (Z = 6) has electron conguration as (1s)
2
(2s)
2
(2p)
2
. There
are three p orbitals with m = 1, 0, 1 as l = 1. Two electrons with both spin equal
to 1/2 (corresponding to total largest spin S = 1) are in orbital m = 1, 0 with total
maximal M = 1 + 0 = 1, corresponding to L = 1. Hence the ground state term is
3
P
0
. It is less than half-lling, J = |L S| = 0. The other two possible terms are
1
S and
1
D. They correspond to higher energies. Do you know how to obtain these
terms? Hint: Use symmetry argument.
Example. Nitrogen (Z = 7): He(2s)
2
(2p)
3
. Three electrons with total spin
S = 3/2 are in states m = 1, 0, 1 with total maximal M = 0 corresponding to
L = 0. Ground state term is therefore
4
S
3/2
. Other terms are
2
P and
2
D.
Example. Oxygen (Z = 8): He(2s)
2
(2p)
4
. Equivalent to two holes (two missing
electrons for lled shell) in 2p orbitals. Its ground state term is therefore same as
carbon,
3
P. However, as it is more than half-lling, J = L +S = 2. So we have
3
P
2
for its ground state.
Example. Boron (Z = 5) and uorine (Z = 9) have similar term but dierent J
values, due to electron-hole symmetry. Can you write down their electron congura-
tions and gure out their ground state terms?
Notice the particle-hole symmetry discussed in the last two examples. A hole is
equivalent to an electron in its quantum nature; it is dened as the missing electron(s)
for the otherwise lled shell.
2.4 Ground state of helium atom
There two electrons in a helium atom and we are dealing with two identical particles.
Consider in general helium-like ions with the following Hamiltonian describing two
electrons interacting each other and with a nucleus containing Z protons
H =
h
2
2m
2
1
h
2
2m
2
2
Ze
2
4
0
_
1
r
1
+
1
r
2
_
+
e
2
4
0
1
r
12
.
As a rst approximation, we want to estimate the ground state energy of this Helium
atom by applying approximate two-body state of Slater determinant discussed earlier,
0
=
1
2
[
1
(x
1
)
2
(x
2
)
2
(x
1
)
1
(x
2
)] ,
using the knowledge from hydrogen-like ions. Note x includes position and spin, i.e.
x = (r, ) with spin =, and the single body wavefunction (x) is a product of
spatial and spin parts (x) = (r)().
For the spatial wavefunction, we use the eigenstates
nlm
(r) for a single electron
H =
h
2
2m
Ze
2
4
0
1
r
are
1s
(r) = R
10
(r) Y
00
(, ) =
Z
3
a
3
0
e
Zr/a
0
2s
(r) = R
20
(r) Y
00
(, ) =
Z
3
8a
3
0
_
1
Zr
2a
0
_
e
Zr/a
0
...
with
1s
(r) as the ground state, and eigenvalues
E
nl
= E
n
=
e
2
8
0
a
0
Z
2
n
2
, n = 1, 2, .
For the ground state of Helium atom, we want both electrons in the lowest energy
state
1s
(r), and antisymmetry requirement can be realized in the spin part of wave-
function,constructed from two spin states | or |,
0
(1, 2) =
1s
(r
1
)
1s
(r
2
) (
1
,
2
), (
1
,
2
) =
1
2
(|
1
|
2
|
1
|
2
)
hence (1, 2) = (2, 1). This is a spin-singlet state. Another possible trial state
is the spin-triplet,
0
(1, 2) =
1
2
[
1s
(r
1
)
2s
(r
2
)
2s
(r
1
)
1s
(r
2
)] (
1
,
2
),
(
1
,
2
) = |
1
|
2
,
1
2
(|
1
|
2
+|
1
|
2
) , |
1
|
2
2.4. GROUND STATE OF HELIUM ATOM 49
but this will give higher energy due to the present of the higher level state
2s
(r
1
).
(It is quite easy to test experimentally if the ground state Helium is singlet or triplet.)
Using the singlet state
t
(1, 2), we evaluate the energy expectation value
_

H
_
= 2
__
h
2
2m
2
1
Ze
2
4
0
1
r
1
__
+
e
2
4
0
_
1
r
12
_
= 2
_
Z
2
e
2
8
0
a
0
_
+
5
4
Ze
2
8
0
a
0
=
_
2Z
2
+
5
4
Z
_
Ry, Ry =
e
2
8
0
a
0
= 5.50 Ry, Z = 2
which is only 6% above the experimental result of 5.81 Ry. In the rst line of the
above equation, evaluation of < 1/r
12
> is nontrivial. See the following math note.
Math Note: Evaluation of
_
1
r
12
_
In this note, we evaluate the following integral from Helium problem,
_
1
r
12
_
=
1
2
_
Z
a
0
_
6 _
d
3
r
1
d
3
r
1
1
|r
1
r
2
|
e
2Z(r
1
+r
2
)/a
0
.
First we use the expression (Fourier transformation)
1
|r
1
r
2
|
=
_
d
3
k
(2)
3
e
ik(r
1
r
2
)
4
k
2
hence
_
1
r
12
_
=
1
2
_
Z
a
0
_
6 _
d
3
k
(2)
3
4
k
2
_
d
3
r
1
e
ikr
1
2Zr
1
/a
0
2
now
_
d
3
r
1
e
ikr
1
2Zr
1
/a
0
=
16Z/a
0
_
k
2
+ (2Z/a
0
)
2
_
2
and nally
_
1
r
12
_
=
4Z
a
0
_

0
dx
(x
2
+ 1)
4
=
5
8
Z
a
0
.

Angular Momentum

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Angular Momentum

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Chapter 2

Angular Momentum, Hydrogen

2.1. ANGULAR MOMENTUMAND ADDITIONOF TWOANGULAR MOMENTA25

similarly we can derive the x- and y-components as

+cot cos sin

cot cos sin

when acting on |l, m. We divide the whole

(l, m) are constants. Therefore, the states |l, m with m = 0, 1, 2,

repeatedly, we obtain the general spherical harmonic, Y

(c) Next, consider state with m = l

S. Write this operator as

2. By directly applying the Hamiltonian

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