Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

TL;DR

This paper evaluates the accuracy of the random-phase approximation (RPA) for many-body noncovalent systems, specifically methane in a water cage, and proposes a hybrid computational approach combining CCSD(T) and RPA for improved large-system predictions.

Contribution

It demonstrates how RPA errors relate to DFT input quality and introduces a combined CCSD(T)-RPA method for efficient large-system energy calculations.

Findings

RSE corrections improve RPA accuracy across various DFT models.

Including singles in RPA corrects sign errors in many-body energies.

Replacing compact clusters with CCSD(T) yields high-accuracy interaction energies.

Abstract

The many-body expansion (MBE) of energies of molecular clusters or solids offers a way to detect and analyze errors of theoretical methods that could go unnoticed if only the total energy of the system was considered. In this regard, the interaction between the methane molecule and its enclosing dodecahedral water cage, CH$_4$(H$_2$O)$_{20}$, is a stringent test for approximate methods, including density-functional theory (DFT) approximations. Hybrid and semilocal DFT approximations behave erratically for this system, with three- and four-body nonadditive terms having neither the correct sign nor magnitude. Here we analyze to what extent these qualitative errors in different MBE contributions are conveyed to post-Kohn-Sham random-phase approximation (RPA). The results reveal a correlation between the quality of the DFT input states and the RPA results. Moreover, the renormalized singles energy (RSE) corrections play a crucial role in all orders of MBE. For dimers, RSE corrects the RPA underbinding for every tested Kohn-Sham model: generalized-gradient approximation (GGA), meta-GGA, (meta-)GGA hybrids, as well as the optimized effective potential at the correlated level. Remarkably, the inclusion of singles in RPA can also correct the wrong signs of three- and four-body nonadditive energies as well as mitigate the excessive higher-order contributions to the MBE. The RPA errors are dominated by the contributions of compact clusters. As a workable method for large systems, we propose to replace those compact contributions with CCSD(T) energies and to sum up the remaining many-body contributions up to infinity with supermolecular or periodic RPA. As a demonstration of this approach, we show that for RPA(PBE0)+RSE it suffices to apply CCSD(T) to dimers and 30 compact, hydrogen-bonded trimers to get the methane-water cage interaction energy to within 1.6% of the reference value.