Solutions to the Problems 26 1

from (5.132) that that gives the ratio 1:2 for consecutive energy splittings, and
it is no longer the case. To describe the additional shift of the singlet level,
we need a spin operator which acts only on the overall singlet. Such is the
projection operator

It is easy to check that &=o gives zero if applied on S = 1 or S = 2 st$tes,

and it gives a factor 1 when applied to an S = 0 state. In other words, Ps,o
projects onto the singlet subspace.
The new effective Hamiltonian can be written as

(5.140)

It is useful to rewrite the projection operator in the form

1
PS,O = 5 [(Sl s2)2 - 11. (5.141)

Replacing it in (5.140), we get the bilinear-biquadratic exchange Hamiltonian

%,$ = Jia Sr . S2 + Q (Sl*S Z )+~ const. (5.142)

where the biquadratic coupling is given by

+ Uab) + J - 2(U - u a b ) + J ) .
2
(5.143)
2(U
Q is dominated by the term with the smallest denominator 2(U - u a 6 ) + J.
It is not unnatural to assume that U - Ua6 is rather smaller than U ,and it
is perhaps of the same order as J. For a rough estimate, let us adopt our
previous U - u a b = 3J/2. We find

6t4 6t4
Q---- (5.144)
U3 U2J
where the negative term dominates.
Did we miss further, still more complicated coupling terms? In the present
+
case, no: It is easy to convince ourselves that J(S1 S 2 ) &(Sl S2)2 is the
mogt general form of a spin-rotationally invariant two-spin coupling for S = 1