Multi-Level Coupled-Cluster Description of Crystal Lattice Energies.

Abstract

The many-body expansion (MBE) of the lattice energy enables an ab initio description of molecular solids using correlated wave function approximations. However, the practical application of MBE requires computing the large number of n-body contributions efficiently. To this end, we employ a multi-level coupled-cluster approach which adapts the approximation level based on interaction type and intermolecular distance. The high-level method, including connected triple excitations, is applied only to monomer relaxation and dimer interactions roughly within the first and second coordination shells. Long-range dimers and trimers are treated using a simplified coupled-cluster description based on the random-phase approximation (RPA). A key feature is an energy correction which mitigates the underbinding error of the base RPA. Convergence to the bulk limit is accelerated by the addition of the periodic Hartree-Fock correction. The proposed approach is validated against recent diffusion Monte Carlo reference data for the X23 data set, achieving a mean absolute error of 3.1 kJ/mol, i.e., chemical accuracy for absolute lattice energies.