A New Approach to Valence Bond Calculations: CASVB

摘要

We present a new approach to the fully-variational optimization of general types of valence-bond wavefunction. Analogous techniques may be used to generate modern valence-bond representations of CASSCF structure spaces. These various procedures, which we term CASVB, are made possible by a highly efficient algorithm for performing exactly the transformations of full CI spaces that arise from general, non-unitary orbital transformations. As examples, we consider modern valence-bond representations of 'N in AT CASSCF descriptions of methane and diborane, in which the total wavefunction is dominated by covalent structures built from a common product of JV nonorthogonal orbitals. These two cases highlight some of the possible differences that may arise between representations of CASSCF wavefunctions and the corresponding fully-variational valence bond results.