Frozen local hole approximation

TL;DR

The paper introduces the frozen local hole approximation (FLHA), a simplified method for calculating correlation effects in solids and polymers, showing it matches full correlation methods in accuracy and offers computational efficiency.

Contribution

The paper presents the FLHA as a new, efficient approximation method that accurately reproduces results of full correlation calculations for extended systems.

Findings

FLHA yields results in excellent agreement with full MRCI(SD) calculations.

FLHA's leading contributions match those of full correlation treatments.

The method is justified and promising for extended systems.

Abstract

The frozen local hole approximation (FLHA) is an adiabatic approximation which is aimed to simplify the correlation calculations of valence and conduction bands of solids and polymers. Within this approximation correlated local hole states (CLHSs) are explicitely generated by correlating local Hartree-Fock (HF) hole states. The hole orbital and its occupancy is kept frozen during these correlation calculations. Effective Hamilton matrix elements are then evaluated with the above CLHSs; diagonalization finally yields the desired correlation corrections for the cationic hole states. We compare and analyze the results of the FLHA with the results of a full MRCI(SD) (multi-reference configuration interaction with single and double excitations) calculation for two prototype model systems, (H2)n ladders and H-(Be)n-H chains. Excellent numerical agreement between the two approaches is found. Comparing the FLHA with a full correlation treatment in the framework of quasi-degenerate variational perturbation theory reveals that the leading contributions in the two approaches are identical. Thus, the FLHA is well-justified and provides a very promising and efficient alternative to fully correlated wavefunction-based treatments of the valence and conduction bands in extended systems.