A practical post-Hartree-Fock approach describing open-shell metal cluster-support interactions. Application to Cu3 adsorption on benzene/coronene

Abstract

Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up fascinating possibilities in designing new heterogeneous (photo)catalysts as well as functional interfaces between AMCs and biologically relevant molecules. Understanding the nature of AMC–support interactions at molecular-level is essential for optimizing (photo)catalysts performance and designing novel ones with improved properties. Møller–Plesset second-order perturbation theory (MP2) is one of the most cost-efficient single-reference post-Hartree–Fock wave-function-based theories that can be applied to AMC–support interactions considering adequate molecular models of the support, and thus complementing state-of-the-art dispersion-corrected density functional theory. However, the resulting AMC–support interaction is typically overestimated with the MP2 method and must be corrected. The coupled MP2 (MP2C) scheme replacing the uncoupled Hartree–Fock dispersion energy by a coupled dispersion contribution, has been proven to describe accurately van-der-Waals (vdW)-dominated interactions between closed-shell AMCs and carbon-based supports. In this work, the accuracy of a MP2C-based scheme is evaluated in modelling open-shell AMC-cluster interactions that imply charge transfer or other strong attractive energy contributions beyond vdW forces. For this purpose, we consider the interaction of Cu₃ with molecular models of graphene of increasing size (benzene and coronene). In this way, it is shown that subchemical precision (within 0.1 kcal mol⁻¹) is achieved with the modified MP2C scheme, using the explicitly correlated coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)-F12] as a benchmark method. It is also revealed that the energy difference between uncoupled and coupled dispersion terms closely follows benchmark values of the repulsive intramonomer correlation contribution. The proposed open-shell MP2C-based approach is expected to be of general applicability to open-shell atomic or molecular species interacting with coronene for regions of the potential landscape where single-reference electronic structure descriptions suffice.