We begin by writing the variance of the energy as

where is the Hamiltonian as defined in chapter
and is the trial/guiding wavefunction which is to be
optimised. The sum is over a set of 3*N*-dimensional electron
configurations, , is an average energy,

and the reweighting factors, , are given by

The electron configurations are sampled from the starting distribution and then kept fixed throughout the optimisation. This ``correlated sampling'' approach gives a good estimate of the difference in variance between wavefunctions corresponding to different sets of parameters. The process can be used iteratively by using the optimised set of parameters to regenerate a new set of configurations which are then used to perform a new optimisation. This is useful when the reweighting factors differ significantly from unity (see section ). The non-linear optimisations over the multi-dimensional parameter spaces were performed using the NAG\ routine E04FCF. This works by finding the unconstrained minimum of a sum of squares, as in Eq.(), using a modified Newton algorithm that requires the function values only.

Tue Nov 19 17:11:34 GMT 1996