Adaptive multiconfigurational wave functions

Abstract

A method is suggested to build simple multiconfigurational wave functions specified uniquely by an energy cutoff Λ. These are constructed from a model space containing determinants with energy relative to that of the most stable determinant no greater than Λ. The resulting Λ-CI wave function is adaptive, being able to represent both single-reference and multireference electronic states. We also consider a more compact wave function parameterization (Λ+SD-CI), which is based on a small Λ-CI reference and adds a selection of all the singly and doubly excited determinants generated from it. We report two heuristic algorithms to build Λ-CI wave functions. The first is based on an approximate prescreening of the full configuration interaction space, while the second performs a breadth-first search coupled with pruning. The Λ-CI and Λ+SD-CI approaches are used to compute the dissociation curve of N2 and the potential energy curves for the first three singlet states of C2. Special attention is paid to the issue of energy discontinuities caused by changes in the size of the Λ-CI wave function along the potential energy curve. This problem is shown to be solvable by smoothing the matrix elements of the Hamiltonian. Our last example, involving the Cu2O2(2+) core, illustrates an alternative use of the Λ-CI method: as a tool to both estimate the multireference character of a wave function and to create a compact model space to be used in subsequent high-level multireference coupled cluster computations.