Energy Decomposition Analysis for Metal Surface–Adsorbate Interactions by Block Localized Wave Functions

Abstract

The energy decomposition analysis based on block localized wave functions (BLW-EDA) allows to gain physical insight into the nature of chemical bonding, decomposing the interaction energy in (1) a "frozen" term, accounting for the attraction due to electrostatic and dispersion interactions, modulated by Pauli repulsion, (2) the variationally assessed polarization energy and (3) the charge-transfer. This method has so far been applied to gas-and condensed-phase molecular systems. However, its standard version is not compatible with fractionally occupied orbitals (i.e. electronic smearing) and, as a consequence, cannot be applied to metallic surfaces. In this work, we propose a 1 simple and practical extension of BLW-EDA to fractionally occupied orbitals, termed Ensemble BLW-EDA. As illustrative examples, we have applied the developed method to analyze the nature of the interaction of various adsorbates on Pt(111), ranging from physisorbed water to strongly chemisorbed ethylene. Our results show that polarization and charge-transfer both contribute significantly at the adsorption minimum for all studied systems. The energy decomposition analysis provides details with respect to competing adsorption sites (e.g., CO on atop, vs. hollow sites) and elucidates the respective importance of polarization and charge transfer for the increased adsorption energy of H 2 S compared to H 2 O. Our development will enable a deeper understanding of the impact of charge transfer on catalytic processes in general.

Water adlayers on noble metal surfaces: Insights from energy decomposition analysis

“…25,26 Energy decomposition analysis (EDA) is a powerful tool which is mostly applied in molecular chemistry, [27][28][29] but also increasingly in condensed phase 30 and at surfaces. [31][32][33] In particular, we have recently extended the block localized wave function (BLW) technique [34][35][36] to metallic surfaces. 33 The BLW based EDA now allows to decompose the adsorption energy into four terms: deformation, frozen, polarization and charge-transfer, which encompasses electron sharing.…”

On the Possibility of Helium Adsorption in Nitrogen Doped Graphitic Materials

“…In order to rigorously quantify the nature of interactions between He atoms and the M-PHI scaffold, the absolutely localized molecular orbital based energy decomposition analysis (ALMO-EDA), developed by some of us for periodic systems [42][43][44][45] , was conducted. Using ALMO-EDA, the total interaction energy between the He atoms and the M-PHI scaffold is decomposed into chemically meaningful components, as shown in Table 2.…”

Theory-guided materials design: two-dimensional MXenes in electro- and photocatalysis

“…In order to accelerate the development of these catalysts, theoretical insight into the bonding mechanism and the difference compared to transition metal surfaces can be obtained via energy decomposition analysis, recently extended to metallic surfaces. 172 To obtain an atomistic understanding of the working catalyst and promising performance of MXenes in electrocatalysis, efforts towards the inclusion of the electrochemical potential and the influence of the solvent need to be made. 36,37,46,173,174 These efforts are not specific to MXenes, but generally necessary for metallic catalysts.…”