Solutions to the Problems 259

orthogonal to both 12,O)and )1,0),we arrive at

a) Second-order perturbation theory. The application of %hop to the low-

lying (neutral) states leads to high-energy (ionized) states. We find
1 t t
'flhopI1,l) = 2t * 5 [c!atc!at(CfbtC!b& + '2btC2bJ)

t t t t
+ClbtC26t(ClatCla$ + '!%taaJ)] lo)* (5.128)
The zeroth-order neutral state I1,l) gets modified by the small admixture of
a higher-lying state, to which it is connected by the matrix element 2t. The
excited state is a charge excitation since each of its components belongs to
an ionized configuration, with one of the sites containing three electrons. The
+
excitation energy is U J. The energy shift of the S = 1 overall triplet is
obtained from second-order perturbation theory as
4t2
Es=1= -- (5.129)
u+J'
Similarly
1 t t
3ihoPlo,o) = d& * ./s [(c!atclaJ - c,'aJc~a~)(c!~tc!bJ+ %btc2Q)

t
+('Ibt%6& t - C f 6 $ c ~ 6 t ) ( C f a ~ C f+a &c2at%a$)]
t t lo>. (5*130)
The excited state is again composed of singly ionized configurations, thus
second-order perturbation theory yields
6t2
Es=o M -- (5.131)
U+J'
Verifying that for S = 1 spins
-6 for S = 0
2 s l . S ~- 2 =
{ -4 f o r S = l
0 for S = 2
the energies (5.124),(5.129),and (5.131)can be thought of as the eigenenergies
(5.132)

of the effective (spin) Hamiltonian

2t2
312
=
!),s-12. (5.133)
U+J