Hydrogen bonding in infinite hydrogen fluoride and hydrogen chloride chains

TL;DR

This paper investigates hydrogen bonding in infinite HF and HCl chains using high-level ab initio methods, decomposing the energy contributions to better understand and efficiently compute their binding energies.

Contribution

It introduces a decomposition of correlation energy into short- and long-range parts using energy increments, enabling more efficient calculations for solid-state hydrogen-bonded systems.

Findings

Van der Waals constants for two-body dispersion interactions are determined.

Long-range correlation contributions can be summed analytically, reducing computational effort.

Short-range interactions require detailed treatment for accurate binding energy calculations.

Abstract

Hydrogen bonding in infinite HF and HCl bent (zigzag) chains is studied using the ab initio coupled-cluster singles and doubles (CCSD) correlation method. The correlation contribution to the binding energy is decomposed in terms of nonadditive many-body interactions between the monomers in the chains, the so-called energy increments. Van der Waals constants for the two-body dispersion interaction between distant monomers in the infinite chains are extracted from this decomposition. They allow a partitioning of the correlation contribution to the binding energy into short- and long-range terms. This finding affords a significant reduction in the computational effort of ab initio calculations for solids as only the short-range part requires a sophisticated treatment whereas the long-range part can be summed immediately to infinite distances.