Assessing weak hydrogen binding on Ca+ centers: An accurate many-body study with large basis sets

Abstract

Weak H2 physisorption energies present a significant challenge to even the best correlated theoretical many-body methods. We use the phaseless auxiliary-field quantum Monte Carlo method to accurately predict the binding energy of Ca+– 4H2. Attention has recently focused on this model chemistry to test the reliability of electronic structure methods for H2 binding on dispersed alkaline earth metal centers. A modified Cholesky decomposition is implemented to realize the Hubbard-Stratonovich transformation efficiently with large Gaussian basis sets. We employ the largest correlation-consistent Gaussian type basis sets available, up to cc-pCV5Z for Ca, to accurately extrapolate to the complete basis limit. The calculated potential energy curve exhibits binding with a double-well structure.