Modular Approach to Selected Configuration Interaction in an Arbitrary Spin Basis: Implementation and Comparison of Approaches.

Abstract

A modular selected configuration interaction (SCI) code has been developed that is based on the existing Monte-Carlo configuration interaction code (MCCI). The modularity allows various selection protocols to be implemented with ease and allows for fair comparison between wave functions built via different criteria. We have initially implemented adaptations of existing SCI theories, which are based on either energy- or coefficient-driven selection schemes. These codes have been implemented not only in the basis of Slater determinants (SDs) but also in the basis of configuration state functions (CSFs) and extended to state-averaged regimes. This allows one to take advantage of the reduced dimensionality of the wave function in the CSF basis and also the guarantee of pure spin states. All SCI methods were found to be able to predict potential energy surfaces to high accuracy, producing compact wave functions, when compared to full configuration interaction (FCI) for a variety of bond-breaking potential energy surfaces. The compactness of the error-controlled adaptive configuration interaction approach, particularly in the CSF basis, was apparent with nonparallelity errors within chemical accuracy while containing as little as 0.02% of the FCI CSF space. The size-to-accuracy was also extended to FCI spaces approaching one billion configurations.