Nonorthogonal Active Space Decomposition of Wave Functions with Multiple Correlation Mechanisms.

ABSTRACT

The nonorthogonal active space decomposition (NO-ASD) methodology is proposed for describing systems containing multiple correlation mechanisms. NO-ASD partitions the wave function by a correlation mechanism, such that the interactions between different correlation mechanisms are treated with an effective Hamiltonian approach, while interactions between correlated orbitals in the same correlation mechanism are treated explicitly. As a result, the determinant expansion scales polynomially with the number of correlation mechanisms rather than exponentially, which significantly reduces the factorial scaling associated with the size of the correlated orbital space. Despite the nonorthogonal framework of NO-ASD, the approach can take advantage of computational efficient matrix element evaluation when performing nonorthogonal coupling of orthogonal determinant expansions. In this work, we introduce and examine the NO-ASD approach in comparison to complete active space methods to establish how the NO-ASD approach reduces the problem dimensionality and the extent to which it affects the amount of correlation energy recovered. Calculations are performed on ozone, nickel-acetylene, and isomers of µ-oxo dicopper ammonia.