30 Ch.

2 Atoms, Ions, and Molecules

and

3t has to be diagonalized in the subspace $1,. . , ,$4. Let us evaluate

the matrix elements

= Cab - Jab (2.46)

where we have introduced the Coulomb integral

(2.47)

and the exchange integral

Cab is obviously positive; less obviously, so is Jab because it can be

regarded as the self-interaction energy of the exchange charge density
&(r)cpb(r)(a formal proof will be given at the end of the Section).
Note that J a b arose as a "cross-term": e.g., we can take the second
term from the left-hand factor and the first term from the right-hand
factor in (2.46).There is no such cross-term in the corresponding matrix
element with $2, because the spin functions are orthogonal

(2.49)

There is, however, an off-diagonal matrix element connecting &?and $3

(2.50)