ANGULAR MOMENTUM THEORY

Paul E.S. Wormer

Institute of Theoretical Chemistry, University of Nijmegen
Toernooiveld, 6525 ED Nijmegen, The Netherlands
E-mail: pwormer@theochem.kun.nl

I. INTRODUCTION

The best known example of an angular momentum operator is the orbital angular mo-
mentum l associated with a vector r,

l ≡ −ir × ∇r , (1)

also written as
X ∂
li = −i ²ijk rj , with i, j, k = 1, 2, 3 = x, y, z, (2)
jk ∂rk

where ²ijk is the Levi-Civita antisymmetric tensor,



 0 if two or more indices are equal,
²ijk =  1 if ijk is an even permutation of 1 2 3, (3)

−1 if ijk is an odd permutation of 1 2 3.

The nabla operator is: ∇r = (∇1 , ∇2 , ∇3 ) with ∇i = ∂/∂ri .

It is well-known that the li satisfy the commutation relations
X
[li , lj ] ≡ li lj − lj li = i ²ijk lk . (4)
k

Often one takes the latter equations as a definition. Three operators ji that satisfy the
commutation relations (4) are then by definition angular momentum operators.
The importance of angular momentum operators in quantum physics is due to the fact
that they are constants of the motion (Hermitian operators that commute with the Hamil-
tonian) in the case of isotropic interactions and also in the case of the motion of a quantum
system in isotropic space. This will be shown in the next section, where we will derive the
relation between 3-dimensional rotations and angular momentum operators.
In the third section we introduce abstract angular momentum operators acting on ab-
stract spaces, and in the fourth we consider the decomposition of tensor products of these
spaces.
Then we will introduce irreducible tensor operators (angular momentum operators are
an example of such operators) and discuss the celebrated Wigner-Eckart theorem.
In the sixth section we will discuss the concept of recoupling and introduce the 6j-
symbol. In the final section we will show how matrix elements, appearing in the close-
coupling approach to atom-diatom scattering, may be evaluated by an extension of the

1
Wigner-Eckart theorem and that the algebraic (easy) part of the calculation requires the
evaluation of a 6j-symbol.
These notes form the content of a six hour lecture course for graduate students special-
izing in theoretical chemistry. Since obviously six hours are not enough to cover all details
of the program just outlined, most of the derivations are delegated to appendices and were
skipped during the lectures. Furthermore the exposition will be restricted to 3-dimensional
rotations; spin or half-integer quantum numbers will not be discussed.

II. THE CONNECTION BETWEEN ROTATIONS AND ANGULAR MOMENTA

In this section we will subsequently rotate: vectors, functions, operators, and N -particle
systems.

A. The rotation of vectors

A proper rotation of the real 3-dimensional Euclidean space is in one-to-one correspon-

dence with a real orthogonal matrix R with unit determinant. That is, if the vector r 0 is
obtained by rotating r, then

r 0 = Rr, with RT = R−1 and det R = 1. (5)

A product of two proper (unit determinant) orthogonal matrices is again a proper or-
thogonal matrix. The inverse of such a matrix exists and is again orthogonal and has unit
determinant. Matrix multiplication satisfies the associative law

((AB)C) = (A(BC)). (6)

These properties show that the (infinite) set of all orthogonal matrices form a group: the
special (unit determinant) orthogonal group in three dimensions SO(3).
It is well-known that any rotation has a rotation axis. This fact was first proved geomet-
rically by Leonhard Euler1 , and is therefore known as Euler’s theorem. We will prove this
fact algebraically and notice to this end that it is equivalent to the statement that every
orthogonal matrix has an eigenvector with unit eigenvalue. Knowing the following rules for
n × n determinants: det AT = det A, det AB = det A det B and det(−A) = (−1)n det A, we
consider the secular equation of R with λ = 1,
³ ´ ³ ´
det (R − 11) = det (R − 11)T = det RT (11 − R) = det RT det (11 − R)
= det (11 − R) = − det (R − 11) , (7)

so that det (R − 11) = 0 and λ = 1 is indeed a solution of the secular equation of R. Since an
orthogonal matrix is a normal matrix, see Appendix A, it has three orthonormal eigenvectors.
The product of eigenvalues of R being equal to det R = 1, the degeneracy of λ = 1 is either

1 Novi Commentarii Academiae Scientiarium Petropolitanae 20, 189 (1776).

2
one or three. In the latter case R ≡ 11 and the rotation is trivial (any vector is an eigenvector
of 11). The former case proves Euler’s theorem.
We will designate the normalized eigenvector by n. Thus,

Rn = n with |n| = 1. (8)

In other words, any rotation of a vector r can be described as the rotation of r over an angle
ψ around an axis with direction n. Accordingly we write R as R(n, ψ).
Using the components of n, we define the matrix N by
 
0 −n3 n2 X

N ≡  n3 0 −n1 
, i.e. Nij = − ²ijk nk and Nr = n × r. (9)
−n2 n1 0 k

In Appendix B it is shown that

R(n, ψ) = 11 + sin ψ N + (1 − cos ψ)N2 , (10)

where 11 is the 3 × 3 unit matrix.

B. The rotation of functions

Consider an arbitrary function f (r). The rotation operator U (n, ψ) is defined as follows

U (n, ψ)f (r) ≡ f (R(n, ψ)−1 r). (11)

[The inverse of the rotation matrix appears here to ensure that the map R(n, ψ) 7→ U (n, ψ) is
a homomorphism, i.e., to conserve the order in the multiplication of operators and matrices.]
Let us next consider an infinitesimal rotation over an angle ∆ψ. By infinitesimal we
mean that only terms linear in ∆ψ are to be retained: ∆ψ À (∆ψ)2 . We will show in
Appendix C that

U (n, ∆ψ)f (r) = (1 − i ∆ψ n · l)f (r), (12)

where l is defined in Eq. (1). Because of this relation one sometimes refers to n · l as the
generator of an infinitesimal rotation.
Functions of operators can be defined by using the Taylor series of ‘normal’ functions.
For instance, the exponential operator is defined by
∞
X
−iψ n·l 1
e = (−iψ n · l)k . (13)
k=0 k!

Formally one must prove that this series makes sense, i.e., that it converges with respect to
some criterion. We ignore these mathematical subtleties and we also assume that differential
equations satisfied by these operators can be solved in the same manner as for ‘normal’
functions. It is easy to derive a differential equation for U (n, ψ). Since

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 U (n, ψ + ∆ψ)f (r) = U (n, ψ)U (n, ∆ψ)f (r) (14)
= U (n, ψ)(1 − i ∆ψ n · l)f (x), (15)
(16)

we find
dU (n, ψ)
= −iU (n, ψ) n · l, (17)
dψ

which, since U (n, 0) = 1, has the solution

U (n, ψ) = e−iψ n·l . (18)

So, we now have an explicit expression of the rotation operator, defined in (11), which shows
most succinctly the connection with the orbital angular momentum operator l.

C. The rotation of an operator

We will consider the rotation of an operator H(r), where r indicates that H acts on
functions of r. Writing Ψ0 (r) = H(r)Ψ(r), we find

U H(r)Ψ(r) = U Ψ0 (r) = Ψ0 (R−1 r) = H(R−1 r)Ψ(R−1 r) = H(R−1 r)U Ψ(r), (19)

so that the rotated operator is given by

H(R−1 r) = U H(r)U −1 . (20)

Notice the difference with the corresponding Eq. (11) defining the rotation of functions.
Suppose next that H(r) is invariant under rotation: H(r) = H(R−1 r) for all R−1 , then
we find from (20) that

U H(r)U −1 ≡ e−iψ n·l H(r)eiψ n·l = H(r). (21)

Upon expansion of the exponentials we find

X
e−iψ n·l Heiψ n·l = H + iψ[H, n · l] + · · · = H + iψ ni [H, li ] + · · · = H. (22)
i

Since it was assumed that Eq. (21) holds for any n and ψ, we find the very important result
that U (n, ψ)HU (n, ψ)−1 = H if and only if [H, li ] = 0 for i = 1, 2, 3.
Suppose H(r) is the Hamiltonian of a certain one-particle system, for instance a particle
moving in a spherical symmetric field due to a nucleus, or a particle moving in field-free
space, then H(r) is rotationally invariant. The unitary operators U (n, ψ) are symmetry
operators (unitary operators that commute with the Hamiltonian) and the l i are constants
of the motion of such a system.

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 D. The rotation of an N -particle system

The theory of this section was so far derived for the rotation of one vector r, say the
coordinate of one electron. It is easy to generalize the theory to N particles. If we simulta-
neously rotate all coordinate vectors r(α) (α = 1, . . . , N ) around the same axis n and over
the same angle ψ, then the N -particle rotation operator still has the exponential form of
Eq. (18), but the angular momentum operator is now given by
N
X
L= l(α), (23)
α=1

where l(α) = −ir(α) × ∇(α). This is due to the fact that [li (α), lj (β)] = 0 (for α 6= β), so
that the N -particle rotation factorizes into a product of one-particle rotations,
N
Y
e−iψn·L = e−iψn·l(α) . (24)
α=1

If the N particles do not interact, the separate rotation of any coordinate vector is a
symmetry operation, and the angular momenta l(α) are all constants of the motion. If, on
the other hand, the particles do interact via an isotropic interaction potential V (r αβ ), with
rαβ = |r(α) − r(β)|, then obviously only the same simultaneous rotation of all particles
conserves the interparticle distances and commutes with the Hamiltonian. Thus, in the case
of interacting particles only the rotation in Eq. (24) is a symmetry operation and only the
total angular momentum L is a constant of the motion.

E. Exercises

1. We have seen that n is an eigenvector of R(n, ψ) with unit eigenvalue. What are the
other two eigenvalues of this matrix?

2. Given the vector n0 = Sn with orthogonal S. Prove that R(n0 , ψ) = SR(n, ψ)ST .

3. The tetrahedral group T consists of twelve proper (unit determinant) rotation matrices
that map the four vectors
       
1 −1 −1 1
       
1,  −1  ,  1 and  −1  (25)
1 1 −1 −1

onto each other. Give the twelve matrices. Hint: Use Eq. (10) for one 3-fold rotation,
the result of the previous exercise and the fact that RT = R−1 .

4. Prove that R(n, ψ) = exp(ψ N), where n and N are related by Eq. (9). Hint: use that
N3 = −N.

5. Show by expanding and considering the first few terms that eA eB = eA+B if and only if
[A, B] = 0.

5
 III. EIGENSPACES OF j 2 AND j3

We consider an abstract Hilbert space L and assume that it is invariant under the
Hermitian operators ji , i = 1, 2, 3 that satisfy the commutation relations (4), i.e.,
X
[ji , jj ] = i ²ijk jk .
k

In one of the first papers on quantum mechanics1 it was already shown that L decomposes
into a direct sum of subspaces Vαj spanned by orthonormal kets

| α, j, m i, m = −j, . . . , j, (26)

with

j 2 | α, j, m i = j(j + 1)| α, j, m i, (27)

j3 | α, j, m i = m| α, j, m i, (28)
q
j± | α, j, m i = j(j + 1) − m(m ± 1)| α, j, m ± 1 i, (29)
P
where j 2 = i ji2 , and j± = j1 ± ij2 are the well-known step up/down operators. It may
happen that an eigenspace of j 2 , characterized by a certain quantum number j, occurs more
than once in L. The index α resolves this multiplicity. Having made this point, we will from
here on suppress α in our notation.
The proof of the existence of basis (26) is very well-known. Briefly, the main arguments
are:
• As [j 2 , j3 ] = 0, we can find a common eigenvector | a, b i of j 2 and j3 with j 2 | a, b i =
a2 | a, b i and j3 | a, b i = b| a, b i. (Since it is easy to show that j 2 has only non-negative
real eigenvalues, we write its eigenvalue as a squared number).

• Considering the commutation relations [j± , j3 ] = ±j± and [j 2 , j± ] = 0, we find, that

j 2 j+ | a, b i = a2 j+ | a, b i and j3 j+ | a, b i = (b + 1)j+ | a, b i. Hence j+ | a, b i = | a, b + 1 i

• If we apply j+ now k + 1 times we obtain, using j+† = j− , the ket | a, b + k + 1 i with

norm

h a, b + k | j− j+ | a, b + k i = [a2 − (b + k)(b + k + 1)]h a, b + k | a, b + k i. (30)

Thus, if we let k increase, there comes a point that the norm on the left hand side
would have to be negative (or zero), while the norm on the right hand side would still
be positive. A negative norm is in contradiction with the fact that the ket belongs to
the Hilbert space L. Hence there must exist a value of the integer k, such that the ket
| a, b + k i 6= 0, while | a, b + k + 1 i = 0. Also a2 = (b + k)(b + k + 1) for that value of k.

• Similarly l + 1 times application of j− gives a zero ket | a, b − l − 1 i with | a, b − l i 6= 0

and a2 = (b − l)(b − l − 1).

1 M. Born, W. Heisenberg, and P. Jordan, Z. Phys. 35, 557–615 (1926).

6
 • From the fact that a2 = (b + k)(b + k + 1) = (b − l)(b − l − 1) follows 2b = l − k, so
that b is integer or half-integer. This quantum number is traditionally designated by
m. The maximum value of m will be designated by j. Hence a2 = j(j + 1).
• Requiring that | j, m i and j± | j, m i are normalized and fixing phases, we obtain the
well-known formula (29).
The spaces with half-integer j (and m) belong to a spin Hilbert space. In agreement with
what was stated in the introduction, we will not consider half-integer j any further.
We can define a unitary rotation operator, as in Eq. (18)

U (n, ψ) ≡ e−iψ n·j . (31)

An exponential operator is defined by its expansion, cf. Eq. (13). Since the eigenspace V j
of j 2 spanned by the basis (26) is invariant under j1 , j2 , and j3 , it is also invariant under
U (n, ψ) and we can define its matrix with respect to that orthonormal basis
j
X
U (n, ψ)| j, m i = | j, m0 ih j, m0 | U (n, ψ) | j, m i, m = −j, . . . , j. (32)
m0 =−j

Often one writes

j 0
Dm 0 ,m (n, ψ) ≡ h j, m | U (n, ψ) | j, m i, (33)

the so-called Wigner D-matrix.

The unitary D-matrices satisfy certain orthogonality relations. In order to explain this,
we note that the map R(n, ψ) 7→ Dj (n, ψ) is a representation of the group SO(3) carried by
V j . (Strictly speaking we must prove at this point that this map satisfies the homomorphism
condition, but we forgo this proof). The space V j is not only invariant under SO(3), but
also irreducible, which means that we cannot find a proper subspace of V j that is invariant
under {U (n, ψ)}. (We omit the proof of this fact, too). Next, we recall from elementary
group theory the so-called great orthogonality relations for irreducible representations
X µ |G|
λ
Dij (g)−1 Dkl (g) = δλµ δjk δil , (34)
g∈G fλ

where λ and µ label irreducible matrix representations of the finite group G of order |G|.
The number f λ is the dimension of Dλ . These orthogonality relations can be generalized to
certain kinds of groups of infinite order, among which SO(3). In this generalization the sum
over the finite group is replaced by integrals over the parameter space. Because a rotation
around n over the angle 2π − ψ is the same as the rotation over ψ around −n, we cover all
of SO(3) if we restrict ψ to run from 0 to π and n over the unit sphere. So, if θ and φ are
the spherical polar angles of n, the parameter space of SO(3) is

0 ≤ ψ ≤ π, 0 ≤ θ ≤ π, 0 ≤ φ ≤ 2π. (35)

It requires some knowledge of tensor analysis (or Lie group theory) to derive the proper
volume element. Moreover, the actual derivation is tedious, so we give the result without
proof:

7
 Z π Z π Z 2π
dτ = 2(1 − cos ψ) sin θdψdθdφ hence |SO(3)| = dτ = 8π 2 . (36)
0 0 0

The Wigner D-matrices thus satisfy the orthogonality relations

Z Z Z
π π 2π
j1 ∗ j2 8π 2
Dm 0 m (n, ψ) Dm0 m (n, ψ) dτ = δj1 ,j2 δm0 ,m0 δm1 ,m2 , (37)
0 0 0 1 1 22 1 2
2j1 + 1
where we have used that the D-matrix is unitary
j1 ∗ j1 −1
Dm 0 m (n, ψ) = Dm m0 (n, ψ)
1 1
. (38)
1 1

A. Exercises

6. Prove by only using (4) the commutation relations: [j 2 , ji ] = 0 for i = 1, 2, 3 and

[j± , j3 ] = ±j± .

7. Show that j− j+ = j 2 − j3 (j3 + 1), again by only using (4).

8. Show from (10) that R(−n, 2π − ψ) = R(n, ψ).

IV. VECTOR COUPLING

In this section we will indicate operators with a hat (as A), b in order to distinguish clearly
between the operators and their quantum numbers.
Consider two different spaces V j1 and V j2 spanned by | j1 , m1 i, m1 = −j1 , . . . , j1 , and
| j2 , m2 i, m2 = −j2 , . . . , j2 , respectively. The tensor product space V j1 ⊗ V j2 is by definition
the space spanned by the product kets | j1 , m1 i ⊗ | j2 , m2 i ≡ | j1 m1 ; j2 m2 i. The product
space is invariant under the operators Jbi ≡ bji ⊗ 1b + 1b ⊗ bji , i = 1, 2, 3. This means that
the elements of V j1 ⊗ V j2 are mapped onto elements in the space under the action of the
operators, so that we can diagonalize Jb2 = Jb12 + Jb22 + Jb32 and Jb3 on the product space. [The
reason why we would like to do this was pointed out above: it may be that Jb2 is a constant
of the motion and that bj 2 (1) and bj 2 (2) are not]. The two-particle operators Jbi obviously
satisfy the angular momentum commutation relations.
A remark on the notation is in order at this point. In quantum chemistry one usually
writes a two-particle orbital product as ψ(1)φ(2). In mathematics one would write more
often ψ ⊗ φ, i.e., the orbital product is an element of a tensor product space. Notice that
ψ ⊗ φ 6= φ ⊗ ψ just as ψ(1)φ(2) 6= φ(1)ψ(2). Operators on a tensor product space may be
tensor product operators themselves, written as Ab ⊗ B.b Their action is defined by

(Ab ⊗ B)ψ
b b
⊗ φ ≡ (Aψ) b
⊗ (Bφ). (39)

The matrix of this operator is a Kronecker product matrix. In quantum chemistry one would
write this expression as
b
A(1) b
B(2)ψ(1)φ(2) b
= (Aψ(1))( b
Bφ(2)). (40)

8
Clearly the operator bji ⊗ 1b + 1b ⊗ bji ≡ bji (1) + bji (2). Note that the terms commute, which
was already used to arrive at Eq. (24). We will use the quantum chemical as well as tensor
notation, whichever is the most convenient.
As the reasoning by which we decomposed a Hilbert space is valid for any angular
momentum, we know that the product space must contain eigenkets | (j1 j2 )JM i, M =
−J, . . . , J of Jb2 and Jb3 . The pair (j1 j2 ) indicates that the eigenket is formed as a linear
combination of product kets | j1 m1 ; j2 m2 i.
The question now arises which eigenvalues J(J + 1) of Jb2 we may expect in the product
space. This problem was solved (in a different context) by two German mathematicians:
R.F.A. Clebsch1 and P.A. Gordan2 . The quantum number J occurs only once and it satisfies
the triangle condition

|j1 − j2 | ≤ J ≤ j1 + j2 . (41)

The proof of the triangle condition is given in Appendix D. By using the resolution of the
identity on V j1 ⊗ V j2 we can write
j1
X j2
X
| (j1 j2 )JM i = | j1 m1 ; j2 m2 ih j1 m1 ; j2 m2 | (j1 j2 )JM i. (42)
m1 =−j1 m2 =−j2

This is the Clebsch-Gordan series and the coefficients h j1 m1 ; j2 m2 | (j1 j2 )JM i are known as
Clebsch-Gordan (CG) coefficients. Since {| (j1 j2 )JM i} is also an orthonormal basis of the
product space V j1 ⊗ V j2 we can write
j1X
+j2 J
X
| j1 m1 ; j2 m2 i = | (j1 j2 )JM ih (j1 j2 )JM | j1 m1 ; j2 m2 i. (43)
J=|j1 −j2 | M =−J

In Appendix E we give an explicit expression (without proof) for the CG-coefficients, which
shows that they are real numbers. Since the CG-coefficients give a transformation be-
tween orthonormal bases, they constitute a unitary matrix. Moreover, they are real so
that h j1 m1 ; j2 m2 | (j1 j2 )JM i = h (j1 j2 )JM | j1 m1 ; j2 m2 i. Some more properties of the CG-
coefficients are given in Appendix E. In the following we will usually drop the quantum
numbers j1 and j2 standing next to JM in the CG-coefficients because they are superfluous.
The symmetry relations of CG-coefficients (see Appendix E) are awkward and difficult
to remember. Wigner3 introduced the following coefficients, 3j-symbols, that have more
pleasant symmetry properties:
µ ¶
j1 j2 j3 (−1)j1 −j2 −m3
≡ √ h j1 m1 ; j2 m2 | j3 , −m3 i. (44)
m1 m2 m3 2j3 + 1
From the results in Appendix E it follows easily that

1 Theorie der binären algebraische Formen, Teubner, Leipzig, (1872).

2 Uber das Formensystem binärer Formen, Teubner, Leipzig, (1875).
3 Unpublished notes (1940) reprinted in: Quantum Theory of Angular Momentum, L.C. Bieden-
harn and H. van Dam, Academic, New York (1965).

9
 µ ¶ µ ¶ µ ¶
j1 j2 j3 j1 +j2 +j3 j2 j1 j3 j3 j1 j2
= (−1) = , (45)
m1 m2 m3 m2 m1 m3 m3 m1 m2

i.e., the 3j-symbol is invariant under a cyclic (even) permutation of its columns and obtains
the phase (−1)j1 +j2 +j3 upon an odd permutation (transposition) of any two of its columns.
Further
µ ¶ µ ¶
j1 j2 j3 j1 +j2 +j3 j1 j2 j3
= (−1) , (46)
−m1 −m2 −m3 m1 m2 m3

and finally we find directly from Eq. (44) that the 3j-symbol vanishes unless m 1 +m2 +m3 =
0.
It is of importance to see what happens to the matrix of the rotation operator (31),
or rather to its two-particle equivalent, which describes the simultaneous rotation of two
particles over the same axis and around the same angle

U (n, ψ) ≡ e−iψ n·J = e−iψ n·(j (1)+j (2)) ≡ e−iψ n·j ⊗ e−iψ n·j ,
b b b b b
(47)

when we decompose the product space V j1 ⊗ V j2 into eigenspaces of Jb2 . The matrix
h J 0 M 0 | U (n, ψ) | JM i is diagonal in J and J 0 because the spaces spanned by | JM i are
invariant under Jb1 , Jb2 and Jb3 . [Observe that we suppressed (j1 j2 ) in | JM i. It is under-
stood that | JM i belongs to V j1 ⊗V j2 for a fixed pair (j1 , j2 ). The running indices describing
bases are either the pair m1 , m2 , or the pair J, M ]. Introducing twice the resolution of the
identity, we find
b X b
h J 0 M 0 | e−iψ n·J | JM i = h J 0 M 0 | j1 m01 ; j2 m02 ih j1 m01 ; j2 m02 | e−iψ n·J | j1 m1 ; j2 m2 i
m1 m2 m01 m02

×h j1 m1 ; j2 m2 | JM i (48)

from which follows,

X b b
h J 0 M 0 | j1 m01 ; j2 m02 ih j1 m01 | e−iψ n·j (1) | j1 m1 ih j2 m02 | e−iψ n·j (2) | j2 m2 i
m1 m2 m01 m02
b
×h j1 m1 ; j2 m2 | JM i = δJ 0 J h JM 0 | e−iψ n·J | JM i. (49)

This may be rewritten as

X ³ ´
h J 0 M 0 | j1 m01 ; j2 m02 i Dj1 (n, ψ) ⊗ Dj2 (n, ψ) h j1 m1 ; j2 m2 | JM i
m1 m2 m01 m02 ;m1 m2
m0 m0
1 2
J
= δ J 0 J DM 0 M (n, ψ). (50)

Equation (50) shows that the Kronecker product matrix Dj1 (n, ψ) ⊗ Dj2 (n, ψ), which in
principle is a completely filled matrix, is block-diagonalized by means of a unitary similarity
transformation by CG-coefficients. The blocks on the diagonal in the matrix on the left
hand side are labeled by J = |j1 − j2 |, . . . , j1 + j2 , block J being of dimension 2J + 1. It is
also easy to go the other way,

10
 b X
h j1 m01 ; j2 m02 | e−iψ n·J | j1 m1 ; j2 m2 i = h j1 m01 ; j2 m02 | JM 0 i (51)
JM M 0
b
×h JM 0 | e−iψ n·J | JM ih JM | j1 m1 ; j2 m2 i.

This may be rewritten as

³ ´ X
Dj1 (n, ψ) ⊗ Dj2 (n, ψ) = h j1 m01 ; j2 m02 | JM 0 i DM
J
0 M (n, ψ) (52)
m01 m02 ;m1 m2
JM M 0
×h JM | j1 m1 ; j2 m2 i.

We are now in a position to show the following useful relation, which we will need in the
proof of the Wigner-Eckart theorem:
Z
j1 ∗ j2 j3 8π 2
Dm 0 m (n, ψ) Dm0 m (n, ψ)Dm0 m (n, ψ)dτ = h j1 m01 | j2 m02 ; j3 m03 i (53)
11 2 2 3 3 2j1 + 1
×h j1 m1 | j2 m2 ; j3 m3 i,

where the integral and its volume element are defined in Eq. (36). To show this relation we
first use Eq. (52), so that (suppressing integration variables) we get
Z X
j1 ∗ j2 j3
(Dm 0 m ) Dm0 m Dm0 m dτ =
1 2 3
h j2 m02 ; j3 m03 | JM 0 ih JM | j2 m2 ; j3 m3 i (54)
1 2 3
JM 0 M
Z
j1 ∗ J
× (Dm 0 m ) DM 0 M dτ
1
1

By the use of (37) we find

Z
j1 ∗ J 8π 2
(Dm 0 m ) DM 0 M dτ = δj1 J δm0 M 0 δm1 M , (55)
11 1
2J + 1
so that
Z
j1 ∗ j2 j3
X 8π 2
(Dm 0 m ) Dm0 m Dm0 m dτ = δj1 J δm01 M 0 δm1 M
11 2 2 3 3
JM 0 M
2J + 1
×h j2 m02 ; j3 m03 | JM 0 ih JM | j2 m2 ; j3 m3 i
8π 2
= h j2 m02 ; j3 m03 | j1 m01 ih j1 m1 | j2 m2 ; j3 m3 i, (56)
2j1 + 1
which proves Eq. (53).

A. Exercises

9. Evaluate h 20 | 11; 1 − 1 i by the explicit expression in Appendix E.

10. Decompose explicitly the space V 1 ⊗ V 1 by the use of step-down operators. Hint: this
product space is invariant under the transposition P12 . This observation may be used
in the required orthogonalizations.
11. Prove Eqs. (45) and (46) from the relations in Appendix E.

11
 V. THE WIGNER-ECKART THEOREM

The Wigner-Eckart theorem1 is a tool to evaluate matrix elements of tensor operators,

and so we start this section with the introduction of such operators. Let us first consider a
simple example, namely a tensor operator of rank one, also known as a vector operator. We
have seen in Eq. (20) that an arbitrary one-particle operator Q(x) rotates as follows

Q(R(n, ψ)−1 x) = U (n, ψ)Q(x)U (n, ψ)† . (57)

Thus, each component of the coordinate operator transforms in this way, and we can write
−1
R(n, ψ) x = U (n, ψ)xU (n, ψ)† , (58)

or
3
X
U (n, ψ)xi U (n, ψ)† = xj Rji (n, ψ). (59)
j=1

This equation serves as the definition of a vector operator: a vector operator consists of three
components that upon rotation of the system transform among themselves as in Eq. (59).
Another example is ∇r = (∇1 , ∇2 , ∇3 ). Recall that a vector product x × y rotates as a
vector

(Rx) × (Ry) = (det R) R(x × y) (60)

and for a proper rotation det R = 1. It is then evident that the angular momentum defined
as a vector product in Eq. (1) is another example of a vector operator.
It is often convenient to work with spherical vectors, defined by
 
−1 0 1
1
(x1 , x0 , x−1 ) ≡ (x, y, z) S with S = √  0 −i 
 −i √ . (61)
2 0 2 0
Observe that this is the same transformation as between real and complex atomic p-orbitals,
and indeed, the spherical components of a vector are proportional to r Ym1 (θ, φ), where
Ym1 (θ, φ) is a spherical harmonic function and m = 1, 0, −1. Recall that spherical harmonic
functions satisfy the relations (27), (28), and (29), where the angular momentum is the
orbital angular momentum of Eq. (1).
If we compute the matrix of U (n, ψ) on basis of Ym1 (θ, φ), with m = 1, 0, −1, we obtain
the matrix D1 (n, ψ). If we perform the transformation (61) on this matrix, we get R(n, ψ),
i.e.,

S D1 (n, ψ) S† = R(n, ψ) (62)

1 C.Eckart, Rev. Mod. Phys. 2, 305 (1930); E. Wigner, Gruppentheorie und ihre Anwendung auf
die Quantenmechanik der Atomspektren, Vieweg, Braunschweig, 1931. Translated by J.J. Griffin
as: Group Theory and its Application to the Quantum Mechanics of Atomic Spectra, Academic,
New York (1959).

12
and so,
³ ´
S† R(n, ψ) S 1
= Dm 0 m (n, ψ). (63)
m0 m

Using this equation and Eq. (61), we can rewrite Eq. (59) in terms of spherical components,
1
X
U (n, ψ) xm U (n, ψ)† = 1
x m 0 Dm 0 m (n, ψ). (64)
m=−1

We now come to the definition of a spherical tensor operator, which is defined with
respect to a set of axes attached to a quantum mechanical system (an atom, a molecule,
etc.). If the 2j + 1 operators Tmj transform among themselves as
j
X
U (n, ψ)Tmj U (n, ψ)† = j
Tmj 0 Dm 0 m (n, ψ). (65)
m=−j

upon rotation of the system, then the set {Tmj |m = −j, . . . , j} is called an irreducible spher-
ical tensor operator. The adjective ‘irreducible’ refers to the fact that the D-matrices con-
stitute an irreducible matrix representation of SO(3).
A very well-known example of a tensor operator is the electric multipole operator
s
N
l 4π X
Mm ≡ Zα rαl Yml (θα , φα ), (66)
2l + 1 α=1

where rα , θα and φα are the spherical polar coordinates of particle α and Zα is its charge.
From the fact that spherical harmonics are eigenfunctions of l 2 and l3 follows
l
X
U (n, ψ)| Yml i = l
| Yml 0 iDm 0 m (n, ψ), (67)
m0 =−l

and considered as a one-particle multiplicative (local) operator a spherical harmonic satisfies

therefore (65). Hence the multipole operator is a tensor operator, provided we rotate all N
particles simultaneously.
A rank-zero tensor operator has by definition j = 0. Since D 0 is unity, we see that its
definition (65) coincides with Eq. (21), where a rotationally invariant operator was defined.
One also refers to rank-zero operators as scalar operators in analogy to rank-one operators,
which are vector operators.
The following is the famous Wigner-Eckart theorem:

h γ 0 j 0 m0 | Tqk | γjm i = h j 0 m0 | kq; jm ih γ 0 j 0 | |T k | | γj i, (68)

which states that the (2j 0 + 1)(2k + 1)(2j + 1) different matrix elements are all given by a
CG-coefficient (the algebraic part) times a so-called reduced matrix element h γ 0 j 0 | |T j | | γj i,
which contains the dynamics of the problem and hence is the difficult part. We introduced
the extra quantum numbers γ and γ 0 to remind us of the fact that in general j and m are
not sufficient to label a state.
The proof of the Wigner-Eckart theorem is simple. Since U (n, ψ) is unitary, we have

13
 C ≡ h γ 0 j 0 m0 | Tqk | γjm i = h U (n, ψ)γ 0 j 0 m0 | U (n, ψ)Tqk U (n, ψ)† | U (n, ψ)γjm i. (69)

We may integrate both sides of this equation over SO(3). On the left hand side this gives
simply 8π 2 C. In the matrix element on the right hand side we first let U (n, ψ) act in bra,
ket, and on the operator and obtain
X Z
0
8π 2 C = h γ 0 j 0 µ0 | Tqk0 | γjµ i Dµj 0 m0 (n, ψ)∗ Dqk0 q (n, ψ)Dµm
j
(n, ψ)dτ . (70)
µ0 q 0 µ

When we substitute Eq. (53) into Eq. (70) and define the following quantity
1 X
h γ 0 j 0 | |T k | | γj i ≡ h j 0 µ0 | kq 0 ; jµ ih γ 0 j 0 µ0 | Tqk0 | γjµ i, (71)
2j 0 + 1 µ0 q0 µ

which obviously does not depend on µ0 , q 0 or µ, we get

C = h j 0 m0 | kq; jm ih γ 0 j 0 | |T k | | γj i. (72)

This proves the Wigner-Eckart theorem.

The Clebsch-Gordan coefficient arising in the case of a scalar operator is,

h j 0 m0 | 00; jm i = δj 0 j δm0 m . (73)

So, we see that only states of the same j and m quantum numbers mix under a scalar
operator. An example of such an operator is the Hamiltonian H of an atom,

h γ 0 j 0 m0 | H | γjm i = δj 0 j δm0 m h γ 0 j | |H| | γj i (74)

and we see here a confirmation of the fact that j 2 is a constant of the motion of an atom,
as the Hamiltonian matrix on basis of | γjm i is obviously block diagonal. The blocks are
labeled by j and the quantum numbers γ 0 and γ label the rows and columns of the blocks.
Notice also that the matrix element of a scalar operator is independent of m.
As another application of the Wigner-Eckart theorem (68) we discuss the Gaunt series 1 .
This series expresses a coupled product of two spherical harmonics depending on the same
angles as a spherical harmonic,
" #1
X (2l1 + 1)(2l2 + 1) 2
Yml11 (θ, φ)Yml22 (θ, φ)h l1 m1 ; l2 m2 | LM i = h l1 0; l2 0 | L0 iYML (θ, φ).
m1 m2 4π(2L + 1)
(75)

The Gaunt series resembles the CG-series, but differs in the fact that the CG-series pertains
to different coordinates, for instance the coordinate vectors of two different particles. To
prove Eq. (75), we observe that Yµλ (θ, φ) is complete, hence we may write
X X
Yml11 (θ, φ)Yml22 (θ, φ)h l1 m1 ; l2 m2 | LM i = LM
Cλµ Yµλ (θφ), (76)
m1 m2 λµ

1 J.A. Gaunt, Trans. Roy. Soc. A228, 151 (1929).

14
 LM
where Cλµ is an expansion coefficient. Project both sides with h Yml33 | and we get by the
orthonormality of the spherical harmonics
X
h Yml33 | Yml11 | Yml22 ih l1 m1 ; l2 m2 | LM i = ClLM
3 m3
. (77)
m1 m2

Apply the Wigner-Eckart theorem:

h Yml33 | Yml11 | Yml22 i = h l3 | |l1 | | l2 i h l3 m3 | l1 m1 ; l2 m2 i (78)

and use
X
h l3 m3 | l1 m1 ; l2 m2 ih l1 m1 ; l2 m2 | LM i = δl3 L δm3 M . (79)
m1 m2

Then from Eq. (77)

ClLM
3 m3
= h L | |l1 | | l2 iδl3 L δm3 M , (80)

which substituted into (76) gives

X
Yml11 (θ, φ)Yml22 (θ, φ)h l1 m1 ; l2 m2 | LM i = h L | |l1 | | l2 iYML (θ, φ). (81)
m1 m2

In order to determine the reduced matrix element we use the fact that
" #1
2l + 1 2
Yml (0, 0) = δm0 , (82)
4π

and insert this into the left and the right hand side of (81). Thus
" #1 · ¸ 21
(2l1 + 1)(2l2 + 1) 2
2L + 1
h l1 0; l2 0 | L0 i = h L | |l1 | | l2 i , (83)
16π 2 4π

and so
" #1
(2l1 + 1)(2l2 + 1) 2
h L | |l1 | | l2 i = h L0 | l1 0; l2 0 i, (84)
4π(2L + 1)

which, after substitution into (81), proves Eq. (75).

The integral in Eq. (78) is often written in terms of 3j-symbols
" #1 µ ¶µ ¶
(2l1 + 1)(2l2 + 1)(2l3 + 1) 2
l1 l2 l3 l1 l2 l3
h Yml11 | Yml22 | Yml33 i = (−) m1
.
4π 0 0 0 −m1 m2 m3
(85)

This integral is known as a Gaunt coefficient. From the symmetry relation (46) follows
immediately that the matrix element vanishes if l1 + l2 + l3 is odd. Here we see that the
Wigner-Eckart theorem furnishes a selection rule, and, indeed, the providing of selection
rules is one of the important applications of the theorem.

15
 A. Exercise

12. Given that

µ ¶ s µ ¶
1 j j j 1 j j
=− compute . (86)
0 −j j (2j + 1)(j + 1) 1 −j j−1

Hints:
(i) From Eq.(61) follows that
1 1
j11 ≡ − √ (j1 + ij2 ), j01 ≡ j3 , 1
and j−1 ≡ √ (j1 − ij2 ) (87)
2 2

are the components of a vector operator.

(ii) Compute the reduced matrix element h j | |j 1 | | j i from h jj | j01 | jj i and the given
3j-symbol.
1
(iii) Use Eq. (29) and the Wigner-Eckart theorem to compute h j, j − 1 | j−1 | j, j i.

VI. RECOUPLING AND 6j-SYMBOLS

Consider the tensor product space V j1 ⊗ V j2 ⊗ V j3 spanned by

| j1 m1 ; j2 m2 ; j3 m3 i ≡ | j1 m1 i ⊗ | j2 m2 i ⊗ | j3 m3 i,

where the kets satisfy Eqs. (27), (28), and (29). This space is invariant under

Ji = ji (1) + ji (2) + ji (3) ≡ ji ⊗ 1 ⊗ 1 + 1 ⊗ ji ⊗ 1 + 1 ⊗ 1 ⊗ ji with i = 1, 2, 3 = x, y, z.

We may diagonalize J 2 and J3 on this space, which can be done most easily by repeated
Clebsch-Gordan coupling.
There are three essentially different bases of the total space that may be obtained this
way. We can couple first j1 and j2 to angular momentum j12 and then couple this with j3
to J. The basis so obtained consists of kets | ((j1 j2 )j12 j3 )JM i. We can also couple first j2
and j3 and then j1 , which leads to | (j1 (j2 j3 )j23 )JM i and finally we may couple first j1 and
j3 to j13 and then j2 . If the order within one pair-coupling is permuted, we do not obtain
an essentially new basis, but one which has only a different phase (cf. the third symmetry
relation of CG-coefficients in Appendix E). The three different bases of V j1 ⊗ V j2 ⊗ V j3 are
orthonormal, and all three give a resolution of the identity. Thus, for instance,
X
| ((j1 j2 )j12 j3 )JM i = | (j1 (j2 j3 )j23 )JM ih (j1 (j2 j3 )j23 )JM | ((j1 j2 )j12 j3 )JM i. (88)
j23

The Fourier coefficient (overlap matrix element) in Eq. (88) is a recoupling coefficient. We
can look upon this coefficient as a matrix element of the unit operator, which is a scalar
operator, so that by the Wigner-Eckart theorem the recoupling coefficient is diagonal in J
and M and does not depend on M; therefore we will drop M in the recoupling coefficient.
By inserting the definition of the coupled kets into the left and right hand side of Eq. (88)
we can relate the recoupling coefficient to CG-coefficients,

16
 X
| j1 m1 ; j2 m2 ; j3 m3 ih j1 m1 ; j2 m2 | j12 m12 ih j12 m12 ; j3 m3 | JM i
m1 m2 m3 m12
X X
= h (j1 (j2 j3 )j23 )J | ((j1 j2 )j12 j3 )J i | j1 m1 ; j2 m2 ; j3 m3 i
j23 m1 m2 m3 m23

×h j2 m2 ; j3 m3 | j23 m23 ih j1 m1 ; j23 m23 | JM i. (89)

Equating the coefficients of the product kets gives

X X
h j1 m1 ; j2 m2 | j12 m12 ih j12 m12 ; j3 m3 | JM i = h (j1 (j2 j3 )j23 )J | ((j1 j2 )j12 j3 )J i
m12 j23 m23
×h j2 m2 ; j3 m3 | j23 m23 ih j1 m1 ; j23 m23 | JM i. (90)
0
Multiply both sides with h j23 m023 | j2 m2 ; j3 m3 i and sum over m2 and m3 , use the unitarity
of CG-coefficients, i.e.,
X
0
h j23 m023 | j2 m2 ; j3 m3 ih j2 m2 ; j3 m3 | j23 m23 i = δj23
0 j δ m0 m ,
23 23 23
(91)
m2 m3

then multiply both sides by h J 0 M 0 | j1 m1 ; j23

0
m023 i sum over m1 and m023 and use again the
unitarity, we then find (dropping primes)
X
h (j1 (j2 j3 )j23 )J | ((j1 j2 )j12 j3 )J i = h JM | j1 m1 ; j23 m23 ih j23 m23 | j2 m2 ; j3 m3 i
m1 m2 m3 m12 m23
×h j1 m1 ; j2 m2 | j12 m12 ih j12 m12 ; j3 m3 | JM i. (92)

Since the recoupling coefficient is independent of M , we may sum the right hand side over
M , provided we divide by 2J + 1. A 6j-symbol is proportional to the recoupling coefficient,
but somewhat more symmetric:
½ ¾
j3 j12 J 1
= (−1)j1 +j2 +j3 +J [(2j12 + 1)(2j23 + 1)]− 2 h (j1 (j2 j3 )j23 )J | ((j1 j2 )j12 j3 )J i.
j1 j23 j2
(93)

An alternative notation that is often used, is the W -coefficient of Racah:

½ ¾
j1 +j2 +j3 +j4 j1 j2 j5
W (j1 j2 j3 j4 ; j5 j6 ) ≡ (−1) (94)
j4 j3 j6

By Eq. (92) a 6j-symbol is given as a sum of products of four CG-coefficients, or alternatively,

as a sum of products of four 3j-symbols. Since the m quantum numbers in Eq. (92) satisfy
linear relations, e.g. m12 = m1 + m2 , this equation contains in fact only a double sum. Each
CG-coefficient is given by a single summation (cf. Appendix E) and hence a 6j-symbol is
defined as a six-fold summation. Racah1 was able to reduce this six-fold sum to a single sum
by a series of substitutions that were so incredibly ingenious that no-one tried to explain
this ever since. We will not make an attempt either, and simply give Racah’s formula in
Appendix F.

1 G. Racah, Phys. Rev. 62, 438 (1942).

17
 The 6j-symbol satisfies two sets of symmetry relations that are easily derived by the use
of Jucys’s angular momentum diagrams. Because of time limitations we will not give the
derivation, but simply state the results. First, any of the six possible permutations of its
columns leaves a 6j-symbol invariant, thus
½ ¾ ½ ¾ ½ ¾
j1 j2 j3 j2 j1 j3 j2 j3 j1
= = , etc. . (95)
j4 j5 j6 j5 j4 j6 j5 j6 j4
Second, any two elements in the upper row may be interchanged with the elements under-
neath them:
½ ¾ ½ ¾ ½ ¾ ½ ¾
j1 j2 j3 j4 j5 j3 j4 j2 j6 j1 j5 j6
= = = . (96)
j4 j5 j6 j1 j2 j6 j1 j5 j3 j4 j2 j3
The four triangular conditions which must be satisfied by the six angular momenta in the
6j-symbol may be illustrated in the following way:
   d     
 d d d     d   d 
¡ @@ d @ ¡ (97)
   d¡   @ d d   d d¡ 

At the same time these diagrams illustrate the second set of symmetry relations obeyed by
the 6j-symbol.

VII. ATOM-DIATOM SCATTERING

As discussed above, one often meets the case of two subsystems with different configu-
ration spaces, that are in eigenstates of j 2 (1) and j 2 (2) and that are coupled
X
| (j1 j2 )j12 m12 i ≡ | j1 m1 i| j2 m2 ih j1 m2 ; j2 m2 | j12 m12 i with m12 = m1 + m2 , (98)
m1 m2

cf. Eq. (42). An obvious (for the quantum chemist) example is formed by two atomic
electrons in orbitals with quantum numbers l1 and l2 , which are Russell-Saunders coupled
to a total angular momentum L.
A somewhat less obvious example is offered by a scattering complex consisting of a
diatom and an atom. In this section we will discuss the use of the Wigner-Eckart theorem
to compute the angular matrix elements that arise in the coupled channel (close coupling)
approach to scattering. In Fig. 1 we have drawn the coordinates of this complex, the so-called
Jacobi coordinates.
Fig. 1
The coordinates relevant in atom-diatom
scattering. The vector ~r is along the diatom
and has a length equal to the bondlength.
It has the coordinate vector r with respect
to space-fixed axes, labeled by x, y and z.
The vector R~ points from the center of mass
of the diatom to the atom. Its length is the
intersystem distance. This vector has coor-
dinate vector R.

18
 The rotational wave function of a diatomic molecule is Yml (r̂), where r̂ is a unit vector
along ~r. Notice that there is a one-to-one correspondence between r̂ and the spherical polar
angles θ and φ of r, which explains the notation Yml (r̂). The relative motion of the atom and
the diatom is described by spherical waves depending on R̂, i.e., by the functions YML (R̂).
The total angular momentum of the complex is J~ = ~l + L, ~ where ~l is a vector operator
with components −ir × ∇r with respect to the space-fixed frame and the vector operator
~ depending on R, is defined similarly. Remember that J~ is a constant of the motion if
L,
and only if the Hamiltonian is invariant under a simultaneous rotation of ~r and R, ~ that is,
under a rotation of the total collision complex. Because we assume the complex to move in
an isotropic space (no external fields), this is the case. Notice that a rotation of only ~r, (or
~ changes the interaction energy, and hence ~l and L
R) ~ are not constants of the motion, at
least at distances where the interaction is appreciable.1
The atom-diatom interaction can be expanded in terms of Legendre functions Pλ (cos γ)
depending on the angle γ between ~r and R.~ The famous spherical harmonic addition theorem
relates Pλ (cos γ) to spherical harmonics depending on the space-fixed coordinates θ, φ and
Θ, Φ of ~r and R,~ respectively:

Xλ
4π
Pλ (cos γ) = (−1)µ Y−µ
λ
(θ, φ)Yµλ (Θ, Φ). (99)
2λ + 1 µ=−λ

To prove Eq. (99), we first note that the right hand side of this equation is a rotational
invariant. Indeed, since in the usual Condon & Shortley phase convention (−1)µ Y−µ λ
= (Yµλ )∗
P
and because the Wigner D-matrices are unitary, the quantity µ |Yµλ |2 is an invariant.
Alternatively, one can look upon the right hand side of Eq. (99) as being proportional
to a CG coupling of two spherical harmonics to total L = 0, because h λµ; λµ0 | 00 i =
δµ,−µ0 (−1)λ−µ [2λ + 1]−1/2 . Since the right hand side of Eq. (99) is invariant under rotation
of the collision complex, the spherical harmonic addition theorem follows easily by rotating
the whole complex, such that ~r 0 is along the space-fixed z-axis, i.e., r 0 = (0, 0, r). Inserting
(82) we get, using the rotational invariance,

Xλ · ¸1
4π 4π 2
(−1)µ Y−µ
λ
(θ, φ)Yµλ (Θ, Φ) = Y0λ (Θ0 , Φ0 ) = Pλ (cos Θ0 ). (100)
2λ + 1 µ=−λ 2λ + 1

The angle Θ0 is the angle that the rotated vector R ~ 0 makes with the z-axis and hence is
equal to γ.
In the coupled channel approach one projects the Schrödinger equation by a coupled set
of spherical harmonics

1 The attentive reader may note that the interaction is invariant under any rotation of R~ around
~r. However, some Coriolis terms arising in the kinetic energy operator are not invariant under this
~ is not a constant of the motion. When we neglect these small Coriolis
rotation, and hence ~r · L
terms, as one does in the coupled state approximation in scattering theory, we obtain axial rotation
~ In the coupled channel approximation the Coriolis
symmetry with infinitesimal generator ~r · L.
terms are not neglected.

19
 X
| (lL)JM i = Yml (θ, φ)YML (Θ, Φ)h lm; LM | JM i, (101)
mM

and since J and M are good quantum numbers we meet only matrix elements diagonal in
J and M
X
h (l0 L0 )J M | (−1)µ Y−µ
λ
(r̂) Yµλ (R̂) | (lL)J M i = h JM | 00; JM ih (l 0 L0 )J | |Pλ | | (lL)J i.
µ

(102)

As h JM | 00; JM i = 1, the matrix elements are independent of M . The reduced matrix

element can be evaluated by the Wigner-Eckart theorem. In doing so one meets algebraic
coefficients: the 6j-symbols.
Before evaluating the matrix element (102), we will treat general tensor operators and
consider
X
C ≡ h (j10 j20 )J 0 M 0 | (−1)µ T−µ
λ
Sµλ | (j1 j2 )JM i. (103)
µ

Remember that the scalar operator is diagonal in J and M . The tensor operator Tµλ acts
on the first subsystem and Sµλ on the second. We use Eq. (42) in bra and ket and the
Wigner-Eckart theorem [Eq. (68)] to write C,
X
C= (−1)µ h JM | j1 m1 ; j2 m2 ih j20 m02 | λµ; j2 m2 ih j10 m01 | λ, −µ; j1 m1 i
µm01 m02 m1 m2

×h j10 m01 ; j20 m02 | JM ih j10 | |T λ | | j1 ih j20 | |S λ | | j2 i. (104)

Substitute
" #1
j2 −j20 −µ 2j20 + 1 2
h j20 m02 | λµ; j2 m2 i = (−1) h j2 m2 | λ, −µ; j20 m02 i, (105)
2j2 + 1
and
0
h j10 m01 | λ, −µ; j1 m1 i = (−)j1 +λ−j1 h j1 m1 ; λ, −µ | j10 m01 i (106)

then we find, while replacing µ by −µ,

" #1
2j20 + 1 2
0 0
C= h j10 | |T λ | | j1 ih j20 | |S λ | | j2 i(−1)j1 +j2 −j2 −j1 +λ
2j2 + 1
X
× h JM | j1 m1 ; j2 m2 ih j2 m2 | λµ; j20 m02 ih j1 m1 ; λµ | j10 m01 ih j10 m01 ; j20 m02 | JM i
µm0 m0
1 2
m1 m2
" #1
j1 +j2 −j20 −j10 +λ 2j20 + 1 2
= (−1) h j10 | |T λ | | j1 ih j20 | |S λ | | j2 i
2j2 + 1
×h (j1 (λj20 )j2 )J | ((j1 λ)j10 j20 )J i, (107)

where we used Eq. (92) for the recoupling coefficient. Introducing the 6j-symbol [Eq. (93)]
we finally find for the matrix element (103)

20
 ½ ¾
j2 −j10 −J
1 j0 j10 J
C = (−1) [(2j10 + 1)(2j20 + 1)] 2
h j10 | |T λ
| | j1 ih j20 λ
| |S | | j2 i 2 . (108)
j1 j2 λ

In the case of atom-diatom scattering we have the tensor operators Tµλ = Yµλ (θ, φ) and
Sµλ = Yµλ (Θ, Φ), cf. Eq. (99). The reduced matrix elements are given by (84), so that in total
Eq. (102) becomes
X 0 2λ + 1
h (l0 L0 )J 0 M 0 | (−1)µ Y−µ
λ
(r̂) Yµλ (R̂) | (lL)J M i = δJ 0 J δM 0 M (−1)L−l −J (109)
µ 4π
½ ¾
1 L0 0 0 l0 J
×[(2l + 1)(2L + 1)] h λ0; l0 | l 0 ih λ0; L0 | L 0 i
2 .
l L λ

The right hand side of this equation is known as a Percival-Seaton coefficient1 .

A. Exercise

13. Prove the spherical expansion of a plane wave:

∞
X l
X
eik·r = 4π il jl (kr) (−1)m Yml (r̂) Y−m
l
(k̂), (110)
l=0 m=−l

where jl (kr) is a spherical Bessel function of the first kind defined by

à !l
l 1 d sin ρ
jl (ρ) ≡ (−ρ) . (111)
ρ dρ ρ

Hints:
(i) Use that Legendre
R1
functions Pl (x) are complete on the interval (−1, 1).
(ii) Use that −1 Pl0 (x)Pl (x)dx = δll0 2/(2l + 1).
(iii) Use the integral representation of the Bessel function:
1 Z π ikr cos θ
jl (kr) = il e Pl (cos θ) sin θdθ. (112)
2 0

(iv) Use the spherical harmonic addition theorem.

1 I.C. Percival and M.J. Seaton, Proc. Camb. Phil. Soc. 53, 654 (1957).

21
 APPENDIX A: EULER’S THEOREM

Basically Euler’s theorem states that any rotation is around a certain axis. We will
generalize this statement to unitary matrices. Remember from linear algebra that an n × n
matrix A can be unitarily diagonalized, (has n orthonormal eigenvectors) if and only if it is
normal, that is, if A satisfies

A† A = AA† . (A1)

The most important examples of normal matrices are Hermitian matrices: A† = A and
unitary matrices: A† = A−1 . Recall that a real unitary matrix is usually referred to as
‘orthogonal matrix’.
Consider the n × n unitary or orthogonal matrix A and its unitary eigenvector matrix U:

U† A U = D with D = diag(λ1 , . . . , λn ). (A2)

Since
³ ´†
U† A U U† A U = D D† = D D∗ = 11, (A3)

we find that λi λ∗i = 1 for i = 1, . . . , n. All eigenvalues of unitary and orthogonal matrices
lie on the unit circle in the complex plane.
Recall further the fundamental theorem of algebra: a polynomial Pn (x) of degree n in the
variable x has n roots zi . These roots may be real or complex. Suppose that the coefficients
of Pn (x) are all real. If zi is a root, that is Pn (zi ) = 0, then obviously Pn (zi )∗ = Pn (zi∗ ) = 0
and zi∗ is also a root. Thus, the fundamental theorem of algebra has as a corollary that the
roots of a polynomial with real coefficients are either real or appear in complex conjugate
pairs.
Consider now the secular problem of an orthogonal matrix O: det (O − λ11) = 0. This
equation has n complex roots which, since the elements of O are real, appear in complex
Q
conjugate pairs and lie on the unit circle in the complex plane. Obviously, det O = i λi
is real and hence is ±1. We find that there are two possibilities for a proper (det = +1)
orthogonal matrix:

(i) The dimension n is even, then the eigenvalues 1 are degenerate of even degree and
there is no single invariant vector. (Since zero is even, zero degeneracy is not excluded
and the matrix may not have a unit eigenvalue at all in this case).

(ii) The dimension n is odd, then the eigenvalues 1 are degenerate of odd degree, so there
is at least one invariant vector.

If we return to the case n = 3 then we see that the eigenvalue 1 of R either occurs with
multiplicity 3, and R ≡ 11, or with multiplicity 1 and then the corresponding eigenvector n
is uniquely determined. This proves Euler’s theorem.

22
 APPENDIX B: PROOF OF EQUATION (10)

Decompose r into a component parallel to the invariant unit vector n and a component
x⊥ perpendicular to it:

r = (r · n) n + x⊥ with x⊥ = r − (r · n) n. (B1)

The vectors x⊥ , y ⊥ ≡ n × r , and n form a right-handed frame. The vector n has unit
length by definition and the vectors x⊥ and y ⊥ both have the length |r|2 − (n · r)2 (which
is not necessarily unity). When we rotate r around n its component along n is unaffected
and its perpendicular component transforms as

x⊥ → cos ψx⊥ + sin ψy ⊥ . (B2)

Hence,

R(n, ψ)r = cos ψ[r − (r · n) n] + sin ψ n × r + (r · n) n. (B3)

We have already seen that

n × r = N r, (B4)

where N is given in Eq. (9). The dyadic product n ⊗ n is a matrix with i, j element equal
to ni nj . Evidently,

(r · n) n = n ⊗ n r. (B5)

By direct calculation one shows that

N2 = n ⊗ n − 11. (B6)

By substituting (B4), (B5) and (B6) into (B3) we obtain finally

R(n, ψ)r = [11 + sin ψ N + (1 − cos ψ)N2 ]r, (B7)

from which Eq. (10) follows, because r is arbitrary.

APPENDIX C: PROOF OF EQUATION (12)

Let us write the infinitesimally rotated function as follows

f˜(r; ∆ψ) ≡ U (n, ∆ψ)f (r) = f (r 0 ), (C1)

where r 0 ≡ R(n, ∆ψ)−1 r. Since ∆ψ is infinitesimal, f˜(r; ∆ψ) can be written in the following
two-term Taylor series
à !
df˜(r; ψ)
f˜(r; ∆ψ) = f˜(r; 0) + ∆ψ . (C2)
dψ ψ=0

23
Because of (C1) we have f˜(r; 0) = f (r). In order to evaluate the derivative in Eq. (C2) we
apply the chain rule to the rightmost term of Eq. (C1)
à ! à ! à ! à !
df˜(r; ψ) df (r 0 ) X ∂f dri0
= = . (C3)
dψ ψ=0
dψ ψ=0 i ∂ri0 ψ=0
dψ ψ=0

Obviously, (∂f /∂ri0 )ψ=0 = ∂f /∂ri . Using Eq. (10) we find

à ! à !
dr 0 d R(n, ψ)−1
= r = −N r. (C4)
dψ ψ=0
dψ ψ=0

Invoking Eq. (9), we now find

à !
df˜(r; ψ) X ∂f X ∂
=− Nij rj = ²ijk nk rj f (r). (C5)
dψ ψ=0 ij ∂ri ijk ∂ri

Because of Eq. (2) this equation can be rewritten in terms of the lk ,

à !
df˜(r; ψ) X
= −i nk lk f (r), (C6)
dψ ψ=0 k

and substitution of this result into (C2) finally gives

f˜(r; ∆ψ) = f (r) − i∆ψ n · lf (r), (C7)

which is the required result.

APPENDIX D: PROOF OF THE TRIANGULAR CONDITION

We shall show that

|j1 − j2 | ≤ J ≤ j1 + j2 . (D1)

As stated in the main text, the (2j1 + 1)(2j2 + 1) dimensional product space V j1 ⊗ V j2
spanned by | j1 , m1 ; j2 , m2 i, (m1 = −j1 , . . . , j1 , and m2 = −j2 , . . . , j2 ), is invariant under J 2
and J3 . This means that both operators can be diagonalized simultaneously on this space.
Product kets are automatically eigenkets of J3 with eigenvalue M = m1 + m2 , so that it
suffices to diagonalize J 2 on the eigensubspaces of J3 contained in V j1 ⊗ V j2 . We will discuss
how, in principle, bases of the eigenspaces of J 2 can be constructed.
In order to see which subspaces occur we consider Fig. 2, where we give an example for
j1 = 3 and j2 = 2.

24
 Fig. 2
Schematic representation of the basis of the product space
with j1 = 3 and j2 = 2. Each dot represents a product
ket | 3, m1 ; 2, m2 i. The quantum numbers m1 and m2 are
given on the lefthand side and on the top of the diagram,
respectively. On the righthand side and at the bottom of
the diagram we find M = m1 + m2 .
The hooks represent eigenspaces of J 2 , see text for de-
tails.

Evidently, there is only one product ket | j1 , j1 ; j2 , j2 i of maximum M , Mmax = j1 + j2 ,

i.e., this eigenspace of J3 is one dimensional and the eigenproblem of J 2 on this space
is also one-dimensional. In other words, | j1 , j1 ; j2 , j2 i is automatically an eigenvector of
J 2 . In Fig. 2 this is the ket in the upper righthand corner with Mmax = 5. Acting with
J+ ≡ j+ (1) + j+ (2) onto this ket, we generate zero, and hence | j1 , j1 ; j2 , j2 i is indeed an
upper rung. The J quantum number of a ladder being equal to its highest M quantum
number, this ladder is characterized by the quantum number J = Mmax = j1 + j2 , [i.e., all
rungs are eigenkets of J 2 with eigenvalue (j1 + j2 )(j1 + j2 + 1)]. The lower rungs may be
generated by repeated action of J− .
In Fig. 2 we see that the second highest eigenvalue of J3 (M = 4) occurs twice, so that
the corresponding eigenproblem of J 2 is of dimension two. However, we already found one
eigenvector, namely | j1 + j2 , j1 + j2 − 1 i ≡ J− | j1 + j2 , j1 + j2 i, so that a diagonalization of
J 2 is unnecessary. (Notice parenthetically that we use the notation | JM i for the coupled
ket, suppressing j1 and j2 ). We only have to find a ket in the two-dimensional space that is
orthogonal to | j1 + j2 , j1 + j2 − 1 i; this will be an eigenfunction of J 2 .
It is easy to see that this orthogonalized function will again be the highest M state
of a ladder of eigenkets of J 2 . Indeed, write briefly | ψ i = | j1 + j2 , j1 + j2 − 1 i and the
orthogonalized function as | φ i, then action of J+ onto | φ i must give an eigenfunction of
J3 with eigenvalue Mmax , i.e., a function proportional to J+ | ψ i, or zero. The former case is
excluded because

h J+ φ | J+ ψ i = h φ | J− J+ | ψ i = h φ | J 2 − J3 (J3 + 1) | ψ i = 0, (D2)

which follows from | ψ i being an eigenfunction of J 2 and J3 , together with the orthogonality
h φ | ψ i = 0. Hence J+ | φ i = 0 does not have a non-zero component along J+ | ψ i. The
highest rung | φ i having M = j1 + j2 − 1, the whole ladder generated by acting with J− is
characterized by J = j1 +j2 −1. Since the eigenspace of J3 with Mmax −1 is two-dimensional,
the eigenvalue j1 + j2 − 1 occurs only once in the product space.
The third highest eigenspace of J3 (M = 3 in the example) is of dimension three. In
this space we already found two eigenvectors of J 2 by the laddering technique. Orthogonal-
izing an arbitrary product ket in this space onto both these functions, we will find another
eigenfunction of J 2 . It is easily shown that this function is the highest rung of a ladder with
J = Mmax − 2, so that this quantum number also occurs once only.

25
 We may continue this way and thus prove the triangular conditions. Graphically we may
easily convince ourselves that these relations hold by reinterpreting the dots in Fig. 2. The
number of product kets is the same as the number coupled states (eigenstates of J 2 and J3 ),
j1
X j2
X j1X
+j2 J
X j1X
+j2
dim(V j1 ⊗ V j2 ) = (2j1 + 1)(2j2 + 1) = 1= 1= (2J + 1).
m1 =−j1 m2 =−j2 J=|j1 −j2 | M =−J J=|j1 −j2 |

(D3)
P
[This equation is easily proved by realizing that J (2J +1) is the sum of an arithmetic series
and by using the well-known sum formula for such a series]. Thus, we may let a dot stand
for a coupled state, for instance the dot with coordinates m1 = 2, m2 = 2, will represent
the coupled state J− | 3, 3; 2, 2 i ≡ | 5, 4 i and the dot with m1 = 3, m2 = 1 the state | 4, 4 i
orthogonal to it. Repeatedly acting with J− onto the highest M ket we generate the border
of the diagram, i.e., a hook consisting of the rightmost column and the bottom row. Acting
with J− onto coupled state with coordinates m1 = 3, m2 = 1 we again generate a hook: the
ladder with J = j1 + j2 − 1, and so on. Only the last eigenvalue J = |j1 − j2 | = 1 is not
a hook, but the topmost part of the leftmost column. Alternatively, one can look now at
equation (D3) as a change of summation variables. The sum over m1 and m2 covers the grid
of Fig. 2 row after row, whereas the sum over J runs over the hooks and the sum over M is
within hook J. The latter double sum also covers the grid exactly once.

APPENDIX E: CLEBSCH-GORDAN COEFFICIENTS

The expression below for the CG-coefficients, due to Van der Waerden1 is the most
symmetric one of the various existing forms. Since its derivation is highly non-trivial, it will
not be presented.
h jm | j1 m1 ; j2 m2 i = δm,m1 +m2 ∆(j1 , j2 , j) (E1)
1
X [(2j + 1)(j1 + m1 )!(j1 − m1 )!(j2 + m2 )!(j2 − m2 )!(j + m)!(j − m)!] 2
t
× (−1)
t t!(j1 + j2 − j − t)!(j1 − m1 − t)!(j2 + m2 − t)!
1
× ,
(j − j2 + m1 + t)!(j − j1 − m2 + t)!
where
" #1
(j1 + j2 − j)!(j1 − j2 + j)!(−j1 + j2 + j)! 2
∆(j1 , j2 , j) = , (E2)
(j1 + j2 + j + 1)!
and the sum runs over all values of t which do not lead to negative factorials. This expression
and all relations in this appendix are valid for integer and half-integer indices.
This expression immediately implies that the CG-coefficients satisfy the following sym-
metry properties

1 B.L. van der Waerden, Die Gruppentheoretische Methode in der Quantenmechanik, Springer,
Berlin (1932).

26
 1. h jm | j1 m1 ; j2 m2 i = h j1 m1 ; j2 m2 | jm i,

2. h jm | j1 m1 ; j2 m2 i = (−1)j1 +j2 −j h j, −m | j1 , −m1 ; j2 , −m2 i,

3. h jm | j1 m1 ; j2 m2 i = (−1)j1 +j2 −j h jm | j2 m2 ; j1 m1 i,

" #1
(2j + 1) 2
4. h jm | j1 m1 ; j2 m2 i = h j2 m2 | jm; ϑ(j1 m1 ) i,
(2j2 + 1)
where the time-reversal operator ϑ acts as follows:

| ϑ(j1 m1 ) i ≡ ϑ| j1 m1 i = (−1)j1 −m1 | j1 , −m1 i.

5. For the special case when j = m = 0 the CG-coefficients are equal to

1
h 0 0 | j1 m1 ; j2 m2 i = δj1 j2 δm1 ,−m2 (−1)j1 −m1 (2j1 + 1)− 2 .

Proof:

1. The CG-coefficients are defined as an inner product; their explicit form shows that
they are real. Hence

h jm | j1 m1 ; j2 m2 i = h j1 m1 ; j2 m2 | jm i∗ = h j1 m1 ; j2 m2 | jm i.

2. From the unitarity of the time reversal operator ϑ and the realness of CG-coefficients
follows that

h jm | j1 m1 ; j2 m2 i = h jm |ϑ† ϑ| j1 m1 ; j2 m2 i = h ϑ(jm) | ϑ(j1 m1 ); ϑ(j2 m2 ) i

= (−1)j+j1 +j2 (−1)−(m+m1 +m2 ) h j, −m | j1 , −m1 ; j2 , −m2 i. (E3)

Since m = m1 + m2 and m is a half-integer if and only if j is a half-integer, we find

that
(−1)−(m+m1 +m2 ) = (−1)−2m = (−1)−2j .

3. The explicit form for CG-coefficients, (E1), is invariant with respect to a simultaneous
interchange j1 ↔ j2 and m1 ↔ −m2 , which implies that m = m1 + m2 → −m and
thus

h jm | j1 m1 ; j2 m2 i = h j, −m | j2 , −m2 ; j1 , −m1 i = (−1)j1 +j2 −j h jm | j2 m2 ; j1 m1 i. (E4)

4. Make simultaneous replacements j ↔ j2 and m ↔ −m2 in the explicit expression for

CG-coefficients, Eq. (E1), and change the summation variable t to j1 −m1 −t. Observe
1
that except for the first factor (2j + 1) 2 and the phase (−1)t they leave the expression
(E1) invariant. Thus

27
 " #1
(2j + 1) 2
h jm | j1 m1 ; j2 m2 i = (−1)j1 −m1 h j2 , −m2 | j1 m1 ; j, −m i
(2j2 + 1)
" #1
(2j + 1) 2
= (−1)j1 −m1 h j2 m2 | jm; j1 , −m1 i
(2j2 + 1)
" #1
(2j + 1) 2
= h j2 m2 | jm; ϑ(j1 m1 ) i. (E5)
(2j2 + 1)

5. Follows by applying the previous rule to the identity

h j1 m1 | j2 m2 ; 00 i = δj1 j2 δm1 m2 .

APPENDIX F: THE 6J-SYMBOL

The following relation is due to Racah:

½ ¾ X
j1 j2 j3
= ∆(j1 j2 j3 )∆(j1 j20 j30 )∆(j10 j2 j30 )∆(j10 j20 j3 ) (−1)t (t + 1)!
j10 j20 j30 t
h
× (t − j1 − j2 − j3 )!(t − j1 − j20 − j30 )!(t − j10 − j2 − j30 )!
×(t − j10 − j20 − j3 )!(j1 + j2 + j10 + j20 − t)!
i−1
×(j1 + j3 + j10 + j30 − t)!(j2 + j3 + j20 + j30 − t)! , (F1)

where ∆(abc) is defined in Eq. (E2). The sum over t is restricted by the requirement that
the factorials occurring in (F1) are non-negative.

APPENDIX G: FURTHER READING

The first (1931) book on the subject is still highly recommendable: E. Wigner, loc. cit..
It gives also an introduction to group and representation theory.
Around 1960 the following books appeared, several of which saw new editions in the
meantime :

1. A.R. Edmonds, Angular Momentum in Quantum Mechanics, Princeton U.P., Prince-

ton, N.J. (1957). A good introduction, but errs on the distinction between active and
passive rotations.

2. M.E. Rose, Elementary Theory of Angular Momentum, Wiley, New York, 1957. Does
not follow Wigner’s convention, Eq. (11), but has an antihomomorphic definition.

3. U. Fano and G. Racah, Irreducible Tensorial Sets, Academic, New York, (1959).
G. Racah, together with E. Wigner, created the subject. Short readable book with
emphasis on the distinction between standard and contrastandard sets, (also known
as co- and contravariant tensors).

28
 4. D.M. Brink and G.R. Satchler, Angular Momentum, Oxford U.P. London, 1962. A
concise short work, very nice as a reference once one understands the material. Has
also a chapter on Jucys diagrams.

5. A.P. Jucys, I.B. Levinson, and V.V. Vanagas, Mathematical Apparatus of the Theory
of Angular Momentum. Translated from the Russian by A. Sen and A.R. Sen, Israel
Program for Scientific Translations, Jerusalem, (1962). Jucys was a Lithuanian and did
not spell his name in Cyrillic characters, nevertheless his name is often transcribed as
Yutsis. This book is noteworthy for (i) introduction of angular momentum diagrams,
which are inspired by, but not the same as, Feynman/Goldstone/Hugenholtz diagrams.
And (ii) discussion of high 3n-j symbols (recoupling coefficients).

6. L.C. Biedenharn and H. van Dam, Quantum Theory of Angular Momentum, Aca-
demic, New York (1965). A collection of reprints, with the most important ones being
the beautiful 1940 paper by Wigner on the representations of simply reducible groups
and the 1953 paper by J. Schwinger, in which he introduces into group theory boson
creation and annihilation operators as a computational tool. Both papers are otherwise
unpublished.

In 1981 the definitive book on the subject appeared: L.C. Biedenharn and J.D. Louck
Angular Momentum in Quantum Physics, Addison-Wesley, Reading, (1981). This is a very
complete and authoritative work, not very easy, but worth studying carefully. Since it is so
complete, it is easy to overlook some of the basic material in it, such as the Wigner-Eckart
theorem for coupled tensor operators, etc.
A reference work is D.A. Varshalovich, A.N. Moskalev, and V.K. Khershonskii, Quan-
tum Theory of Angular Momentum, translated from the Russian, World Scientific, Singa-
pore (1988). This book has no text, only 508 pages of formulas, all pertaining to angular
momentum theory. Be careful, though, we did find some errors.
Also the book by Zare must be mentioned, R.N. Zare, Angular Momentum, Wiley,
New York (1988), since it is very popular among beginners. However, at some places the
presentation is wrong. Consider Eqs. (1.67) and (3.58), which give for instance for J = 1 and
M = 0 the erroneous
³ result | 1, 0 i = ´αβ. In contrast, the spinfunctions on p. 114 correctly
√
read | 1, 0 i = α(1)β(2) + β(1)α(2) / 2. Equations (1.67) and (3.58) are correct only
for commuting variables, such as complex numbers or boson second-quantized operators;
one-electron spinfunctions do not belong to this class.
Finally, it must be pointed out that A. Messiah, Quantum Mechanics, Vol. II, North
Holland, Amsterdam, (1965) has a very good introduction in Chapter XIII and a good
summary in Appendix C. All sorts of arbitrary conventions enter the quantum theory of
angular momentum, but if you follow Messiah on this you cannot go wrong.

29