title: Exfoliation Energy of Black Phosphorus Revisited: A Coupled Cluster Benchmark.
abstract: Black phosphorus (black-P) consists of phosphorene sheets, stacked by van der Waals dispersion. In a recent study based on periodic local second-order Møller-Plesset perturbation theory (LMP2) with higher-order corrections evaluated on finite clusters, we obtained a value of -151 meV/atom for the exfoliation energy. This is almost twice as large as another recent theoretical result (around -80 meV/atom) obtained with quantum Monte Carlo (QMC). Here, we revisit this system on the basis of the recently implemented, periodically embedded ring coupled cluster (rCCD) model instead of LMP2. Higher-order coupled cluster corrections on top of rCCD are obtained from finite clusters by utilizing our new "unit-cell-in-cluster" scheme. Our new value of -92 meV/atom is noticeably lower than that based on LMP2 and in reasonably close agreement with the QMC result. However, in contrast to QMC, no strong effect from the second-neighbor and farther layers in black-P are observed in our calculations.
authors.affiliation: Institut für Chemie, Humboldt-Universität zu Berlin , Brook-Taylor-Strasse 2, D-12489 Berlin, Germany.
authors.forename: Martin
authors.identifier: http://orcid.org/0000-0002-2688-3214
authors.initials: M
authors.lastname: Schütz
authors.affiliation: Dipartimento di Chimica and NIS (Nanostructured Interfaces and Surfaces) Centre, Università di Torino , via Giuria 5, I-10125 Torino, Italy.
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Maschio
authors.affiliation: Department of Chemistry and Materials Science, Aalto University , Kemistintie 1, 02150 Espoo, Finland.
authors.forename: Antti J
authors.identifier: http://orcid.org/0000-0003-4187-5447
authors.initials: AJ
authors.lastname: Karttunen
authors.affiliation: Institut für Chemie, Humboldt-Universität zu Berlin , Brook-Taylor-Strasse 2, D-12489 Berlin, Germany.
authors.forename: Denis
authors.initials: D
authors.lastname: Usvyat