An effective scheme to determine surface energy and its relation with adsorption energy

Bo Li,Xin Li,Wang Gao,Qing Jiang

doi:10.1016/j.actamat.2021.116895

Abstract

Surface energy is fundamental in controlling surface properties and surface-driven processes like heterogeneous catalysis, as adsorption energy is. It is thus essential to establish an effective scheme to determine surface energy and its relation with adsorption energy. Herein, we propose a model to quantify the effects of materials’ intrinsic characteristics on the material-dependent property and anisotropy of surface energy, based on the period number and group number of bulk atoms, and the valence-electron number, electronegativity and coordination of surface atoms. Our scheme holds for elemental crystals in both solid and liquid phases, body-centered-tetragonal intermetallics, fluorite-structure intermetallics, face-centered-cubic intermetallics, Mg-based single-atom alloys, III-V semiconductors, transition metal carbides, and transition metal nitrides, which further identifies a quantitative relation between surface energy and adsorption energy and rationalizes the material-dependent error of first-principle methods in calculating the two quantities. This model is predictive with easily accessible parameters and thus allows the rapid screening of materials for targeted properties.

Highlights

Surface energy is fundamental and dominant in controlling surface structure, reconstruction, roughening, nanoparticles’ size, and crystal’s shape for solids[1,2,3,4]
As surfaces are the region where materials interact with media, surface energy is of great importance in determining surface-driven processes such as heterogeneous catalysis, gas sensing and biomedical applications[5,6,7,8], as adsorption energy is
We study the origin of the material-dependent error of first-principle methods in calculating surface energy and adsorption energy

Summary

Introduction

Surface energy is fundamental and dominant in controlling surface structure, reconstruction, roughening, nanoparticles’ size, and crystal’s shape for solids[1,2,3,4]. We propose a universal picture to determine surface energy and its correlation with adsorption energy, by using the period number and group number of bulk atoms, and the valence-electron number, electronegativity and coordination number of surface atoms This model is predictive for a variety of materials covering elemental crystals in both solid and liquid phases, alloys, and semiconductor compounds. The description accuracy with Җ is overall improved compared to that with ψ These results imply that the period number and group number of bulk atoms, and the valence-electron number and electronegativity of surface atoms together determine surface energy. This equation quantitatively describes the material-dependent nature and anisotropy of surface energy for solids, and can be used to estimate rapidly the trends of surface energy on different materials and surfaces, as the involved parameters are accessible (see more details in Supplementary Note 1). We study cleavage energies for types of AB intermetallics with different orientations, for types of A2B intermetallics with different orientations and for types of A3B intermetallics with 3 different orientations, and surface energies for 31 Mg-M surface alloys with (0001), (101̅0) and (112̅0) surfaces, and for 12 types of semiconductor compounds with (110) surfaces42-

Discussion

Methods