The junChS and junChS-F12 models: parameter-free efficient yet accurate composite schemes for energies and structures of non-covalent complexes

TL;DR

The paper introduces the junChS-F12 model chemistry, an efficient, parameter-free method that improves the accuracy of interaction energies and structures of non-covalent molecular complexes, outperforming existing schemes.

Contribution

It extends the junChS model to explicitly-correlated F12 methods, providing a reliable, cost-effective approach with improved performance and sub-chemical accuracy for energies and structures.

Findings

junChS-F12 outperforms traditional model chemistries

Achieves sub-chemical accuracy without empirical parameters

Effective for both energetic and structural characterizations

Abstract

A recently developed model chemistry (denoted as junChS [Alessandrini et al J. Chem. Theory Comput. 2020, 16, 988-1006]) has been extended to the employment of explicitly-correlated (F12) methods. This led us to propose a family of effective, reliable and parameter-free schemes for the computation of accurate interaction energies of molecular complexes ruled by non-covalent interactions. A thorough benchmark based on a wide range of interactions showed that the so-called junChS-F12 model, which employs cost-effective revDSD-PBEP86-D3(BJ) reference geometries, has an improved performance with respect to its conventional counterpart and outperforms well-known model chemistries. Without employing any empirical parameter and at an affordable computational cost, junChS-F12 reaches sub-chemical accuracy. Accurate characterizations of molecular complexes are usually limited to energetics. To take a step forward, the conventional and F12 composite schemes developed for interaction energies have been extended to structural determinations. A benchmark study demonstrated that the most effective option is to add MP2-F12 core-valence correlation corrections to fc-CCSD(T)-F12/jun-cc-pVTZ geometries without the need of recovering the basis set superposition error and the extrapolation to the complete basis set.