Abstract
An analytic energy gradient method for second-order quasidegenerate
perturbation theory with multiconfigurational self-consistent field
reference functions (MC-QDPT) is presented. An expression for the
energy gradients is derived using the Lagrange multiplier method. The
gradients are calculated without solving coupled perturbed equations.
Instead, it is necessary to solve eight sets of linear equations for
the multipliers. Six of the eight equations reduces to simple partial
differential forms which directly give the multipliers, and only the
remaining two are large scale linear equations that need iterative
procedure. The gradients are given as the product of the first
derivative integrals and the effective densities that depends on the
obtained multipliers and the parameters. The expression for the
conventional quasidegenerate perturbation theory and numerical
results for the methylene molecule are also presented.