title: Toward an Accurate Estimate of the Exfoliation Energy of Black Phosphorus: A Periodic Quantum Chemical Approach.
abstract: The black phosphorus (black-P) crystal is formed of covalently bound layers of phosphorene stacked together by weak van der Waals interactions. An experimental measurement of the exfoliation energy of black-P is not available presently, making theoretical studies the most important source of information for the optimization of phosphorene production. Here, we provide an accurate estimate of the exfoliation energy of black-P on the basis of multilevel quantum chemical calculations, which include the periodic local Møller-Plesset perturbation theory of second order, augmented by higher-order corrections, which are evaluated with finite clusters mimicking the crystal. Very similar results are also obtained by density functional theory with the D3-version of Grimme's empirical dispersion correction. Our estimate of the exfoliation energy for black-P of -151 meV/atom is substantially larger than that of graphite, suggesting the need for different strategies to generate isolated layers for these two systems.
authors.affiliation: Dipartimento di Chimica and NIS (Nanostructured Interfaces and Surfaces) Centre, Università di Torino , via Giuria 5, I-10125 Torino, Italy.
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Sansone
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: Institute for Physical and Theoretical Chemistry, University of Regensburg , Universitätsstraße 31, D-93040 Regensburg, Germany.
authors.forename: Denis
authors.initials: D
authors.lastname: Usvyat
authors.affiliation: Institute for Physical and Theoretical Chemistry, University of Regensburg , Universitätsstraße 31, D-93040 Regensburg, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Schütz
authors.affiliation: Department of Chemistry, Aalto University , Kemistintie 1, FI-02150 Espoo, Finland.
authors.forename: Antti
authors.initials: A
authors.lastname: Karttunen
keywords: black phosphorus; periodic quantum chemical methods; phosphorene; van der Waals interactions in solids