A fragment method for systematic improvement of anharmonic adsorbate vibrational frequencies: Acetylene on Cu(001)

Chulkov, Sergey K.; Benoit, David M.

Abstract

We suggest a novel method for systematic improvement of anharmonic adsorbate frequencies based on a fragment approach. The calculations are carried out by considering the adsorbed molecule separately and computing an energy correction using high-level ab initio method in addition to a standard calculation of the whole adsorbed system using quantum mechanical techniques with periodic boundary conditions. We demonstrate its reliability for a C 2H2 molecule chemisorbed on a Cu(001) surface. We also show that the accuracy of the presented approach with a suitable description of the periodic surface depends mainly on the accuracy of the high-level ab initio method used to describe the adsorbate molecule. Moreover, our technique potentially allows to predict adsorbate vibrational spectra with spectroscopic accuracy. © 2013 AIP Publishing LLC.

Citation

Chulkov, S. K., & Benoit, D. M. (2013). A fragment method for systematic improvement of anharmonic adsorbate vibrational frequencies: Acetylene on Cu(001). The Journal of chemical physics, 139(21), Article 214704. https://doi.org/10.1063/1.4829461

• Journal Article Type: Article
• Acceptance Date: Oct 25, 2013
• Online Publication Date: Dec 4, 2013
• Publication Date: Dec 7, 2013
• Deposit Date: Jun 8, 2022
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 139
• Issue: 21
• Article Number: 214704
• DOI: https://doi.org/10.1063/1.4829461
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://hull-repository.worktribe.com/output/502526