Bridging molecular dynamics and correlated wave-function methods for accurate finite-temperature properties

Abstract

We introduce the "selPT" perturbative approach, based on ab initio molecular dynamics (AIMD), for computing accurate finite-temperature properties by efficiently using correlated wave-function methods. We demonstrate the power of the method by computing prototypical molecular enthalpies of adsorption in zeolite (CH4 and CO2 on protonated chabazite at 300 K) using the random phase approximation. Results are in excellent agreement with experiment. The improved accuracy provided by selPT represents a crucial step towards the goal of truly quantitative AIMD predictions of experimental observables at finite temperature.