Vibrational signature of a single water molecule adsorbed on Pt(111): toward a reliable anharmonic description

Benoit, David M.

Abstract

In this study, we present a thorough benchmarking of our direct anharmonic vibrational variation-perturbation approach for adsorbed molecules on surfaces. We then use our method to describe the vibrational structure of a water molecule adsorbed on a Pt(111) surface and compare our results with the available experimental data. By using an explicitly correlated hybrid method to describe the molecule-surface interaction, we improve on the initial periodic PBE/DZP potential energy landscape and obtain vibrational frequencies that are of near-experimental accuracy. We introduce an implementation of anharmonic z-polarized IR intensity calculation and explain the absence of antisymmetric O-H stretch in the experimental data for the adsorbed water molecule, while the symmetric O-H stretch is predicted to be visible.

Citation

Benoit, D. M. (2015). Vibrational signature of a single water molecule adsorbed on Pt(111): toward a reliable anharmonic description. The journal of physical chemistry. A, 119(47), 11583-11590. https://doi.org/10.1021/acs.jpca.5b08543

• Journal Article Type: Article
• Acceptance Date: Nov 4, 2015
• Online Publication Date: Nov 16, 2015
• Publication Date: Nov 4, 2015
• Deposit Date: Dec 11, 2015
• Publicly Available Date: Nov 23, 2017
• Journal: Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
• Print ISSN: 1089-5639
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 119
• Issue: 47
• Pages: 11583-11590
• DOI: https://doi.org/10.1021/acs.jpca.5b08543
• Keywords: Direct anharmonic vibrational variation–perturbation, Adsorbed molecules on surfaces
• Public URL: https://hull-repository.worktribe.com/output/382461
• Publisher URL: http://pubs.acs.org/doi/abs/10.1021/acs.jpca.5b08543
• Contract Date: Nov 23, 2017