120 j 4 ANGULAR MOMENTUM

have the choice of first coupling j1 to j2 to form j1,2 and then coupling j3 to
that to give the overall resultant j.

Illustration 4.2 Coupling several momenta

Consider the total orbital angular momenta of three p-electrons. The coupling
of one pair gives l1,2 ¼ 2, 1, 0. Then the third couples with each of these
resultants in turn: l1,2 ¼ 2 gives rise to L ¼ 3, 2, 1; l1,2 ¼ 1 gives rise to L ¼
2, 1, 0; and l1,2 ¼ 0 gives rise to only L ¼ 1. The angular momentum states
are therefore F þ 2D þ 3P þ S.

When there are more than two sources of angular momentum, the overall
states may be formed in different ways. Thus, instead of the scheme described
above, j1 and j3 can first be coupled to form j1,3, and then j2 coupled to j1,3 to
form j. The triangle condition applies to each step in the coupling procedure,
but the compositions of the states obtained are different. The states obtained
by the first coupling procedure can be expressed as linear combinations of the
states obtained by the second procedure, and the expansion coefficients are
known as Racah coefficients or, in slightly modified form, as ‘6j-symbols’.
The question of alternative coupling schemes, and how to select the most
appropriate ones, arises in discussions of atomic and molecular spectra, and
we shall meet it again there.

PROBLEMS
4.1 Evaluate the commutator [lx,ly] in (a) the position satisfy the angular momentum commutation relations
representation, (b) the momentum representation. when we write sq ¼ 12!hsq, and hence provide a matrix
representation of angular momentum. (b) Why does the
4.2 Evaluate the commutators (a) [ly2 ,lx], (b) [ly2 ,lx2 ], and
representation correspond to s ¼ 12? Hint. For the second
(c) [lx,[lx,ly]]. Hint. Use the basic commutators in eqn 4.7.
part, form the matrix representing s2 and establish its
4.3 Confirm that [l2, lx] ¼ 0. eigenvalues.
4.4 Verify that eqn 4.9 expresses the basic angular 4.7 Using the Pauli matrix representation, reduce each of
momentum commutation rules. Hint. Expand the left of the operators (a) sxsy, (b) sxs2y s2z , and (c) s2x s2y s2z to a single
eqn 4.9 and compare coefficients of the unit vectors. Be spin operator.
careful with the ordering of the vector components when
4.8 Evaluate the effect of (a) eisx =!h , (b) eisy =!h , (c) eisz =!h on
expanding the determinant: the operators in the second row
an a spin state. Hint. Expand the exponential operators
always precede those in the third.
as in Problem 1.15 and use arguments like those in
4.5 Verify that the five matrices in eqn 4.37 yield Problem 4.7.
the correct results for the applications of the
4.9 Suppose that in place of the actual angular momentum
spin operators sq (q ¼ x, y, z, þ , # ) on the spin states
commutation rules, the operators obeyed [lx,ly] ¼ # i !
hlz.
a and b.
What would be the roles of l$?
4.6 (a) Confirm that the Pauli matrices
4.10 Calculate the matrix elements (a) h0,0jlzj0,0i,
2
! " ! " ! "
0 1 0 #i 1 0 (b) h2,1jlþ j2,0i, (c) h2,2jlþ j2,0i, (d) h2,0jlþ l # j2,0i,
sx ¼ sy ¼ sz ¼ 2 2
1 0 i 0 0 #1 (e) h2,0jl # lþ j2,0i, and (f) h2,0jl# lz lþ j2,0i.
 PROBLEMS j 121

4.11 Demonstrate that j1 # j2 is not an angular and check the answer against the values in Appendix 2.
momentum. For the matrix element, express the coupled states in the
uncoupled representation, and then operate with j1z.
4.12 Calculate the values of the following matrix elements
between p-orbitals: (a) hpxjlzjpyi, (b) hpxjlþ jpyi, (c) hpzjlyjpxi, 4.21 Use the vector model of angular momentum to
(d) hpzjlxjpyi, and (e) hpzjlxjpxi. derive the value of the angle between the vectors
representing (a) two a spins, (b) an a and a b spin in a
4.13 Evaluate the matrix elements (a) h j; mj þ 1jj3x jj; mj i
state with S ¼ 1 and MS ¼ þ1 and MS ¼ 0, respectively.
and (b) h j; mj þ 3jj3x jj; mj i.
4.22 Set up a quantum mechanical expression that can be
4.14 Verify eqn 4.31 for the shift operators in spherical
used to derive the same result as in Problem 4.21. Hint.
polar coordinates. Use eqn 4.30.
Consider the expectation value of s1 & s2.
4.15 Confirm that the spherical polar forms of the
4.23 Apply both procedures (of the preceding two
orbital angular momentum operators in eqn 4.30 satisfy
problems) to calculate the angle between a spins in the aaa
the angular momentum commutation relation [lx, ly] ¼ i !hlz
state with S ¼ 32.
and that the shift operators in eqn 4.31 satisfy
[lþ , l# ] ¼ 2!hlz. 4.24 Consider a system of two electrons that can have
either paired or unpaired spins (e.g. a biradical). The
4.16 Verify that successive application of l# to cll with energy of the system depends on the relative orientation
l ¼ 2 in eqn 4.32 generates the five normalized spherical of their spins. Show that the operator (hJ/!h2)s1 & s2
harmonics Y2ml as set out in Table 3.1. distinguishes between singlet and triplet states. The system
4.17 (a) Demonstrate that if [j1q, j2q0 ] ¼ 0 for all q, q 0 , is now exposed to a magnetic field in the z-direction.
then j1 % j2 ¼ # j2 % j1. (b) Go on to show that if j1 % j1 ¼ i!hj1 Because the two electrons are in different environments,
and j2 % j2 ¼ i!hj2, then j % j ¼ i !
hj where j ¼ j1 þ j2. they experience different local fields and their interaction
energy can be written (mB/!h)b(g1s1z þ g2s2z) with g1 6¼ g2; mB
4.18 In some cases mj1 and mj2 may be specified at the is the Bohr magneton and g is the electron g-value,
same time as j because although [j2,j1z] is non-zero, the quantities discussed in Chapter 13. Establish the matrix
effect of [j2,j1z] on the state with mj1 ¼ j1, mj2 ¼ j2 is zero. of the total hamiltonian, and demonstrate that when
Confirm that [j2,j1z]jj1j1; j2j2i ¼ 0 and [j2,j1z]jj1, # j1; hJ >> mBb, the coupled representation is ‘better’, but that
j2, # j2i ¼ 0. when mBb >> hJ, the uncoupled representation is ‘better’.
4.19 Determine what total angular momenta may arise in Find the eigenvalues and eigenstates of the system in
the following composite systems: (a) j1 ¼ 3, j2 ¼ 4; (b) the each case.
orbital momenta of two electrons (i) both in p-orbitals, 4.25 What is the expectation value of the z-component of
(ii) both in d-orbitals, (iii) the configuration p1d1; orbital angular momentum of electron 1 in the jG,MLi state
(c) the spin angular momenta of four electrons. Hint. of the configuration d2? Hint. Express the coupled state in
Use the Clebsch–Gordan series, eqn 4.44; apply it terms of the uncoupled states, find hG,MLjl1zjG,MLi in
successively in (c). terms of the vector coupling coefficients, and evaluate it for
ML ¼ þ4, þ3, . . . , #4.
4.20 Construct the vector coupling coefficients for a
system with j1 ¼ 1 and j2 ¼ 12 and evaluate the matrix 4.26 Prove that mj1,mj2 jCmj1,mj2 j2 ¼ 1 for a given j1, j2, j.
P

elements hj 0 mj 0 jj1zjjmji. Hint. Proceed as in Section 4.12 Hint. Use eqn 4.45 and form hj1j2;jmjjj1j2;jmji.