The true normalized eigenfunctions, , of form a complete basis, so the trial wavefunction, , may be expanded as a linear combination of these eigenfunctions,

with

As the are normalised it follows that is normalised. Using the expansion of to calculate from Eq.() gives

where is the eigenvalue corresponding to eigenstate
. Since for all *n*, it is clear
that

Variational calculations rely on making a physically plausible guess at the form of the ground state wavefunction, , of the Hamiltonian, . This guess will be referred to as the trial/guiding wavefunction throughout this thesis. The ``trial'' part of the name refers to the use of the wavefunction as a guess of the true groundstate wavefunction to be used as the input wavefunction in a Variational quantum Monte Carlo (VMC) calculation. The ``guiding'' part refers to the use of the same wavefunction as an input wavefunction in the Diffusion quantum Monte Carlo (DMC) algorithm as part of the mechanism to introduce importance sampling. This will described in more detail in section . The trial/guiding wavefunction depends on a number of variable parameters which can be adjusted to minimise the energy expectation value. If the guessed values of these parameters are good and the chosen functional form builds in enough variational freedom to adequately describe the physics of the system being studied, then very accurate estimates of the ground state energy can be obtained. Variational quantum Monte Carlo (VMC) calculations are direct applications of the above variational principle.

Tue Nov 19 17:11:34 GMT 1996