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Towards Accurate Spectroscopic Identification of Species at Catalytic Surfaces: Anharmonic Vibrations of Formate on AuPt

Published online by Cambridge University Press:  18 December 2012

Matthew Chan ,
Koichi Yamashita ,
Tucker Carrington  and
Sergei Manzhos
Matthew Chan
Affiliation:
Department of Chemistry and Chemical Biology, McMaster University, Hamilton ON, L8S 4M1, Canada
Koichi Yamashita
Affiliation:
Department of Chemical System Engineering, School of Engineering, University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan
Tucker Carrington
Affiliation:
Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston ON, K7L 3N6, Canada
Sergei Manzhos*
Affiliation:
Department of Mechanical Engineering, Faculty of Engineering, National University of Singapore, Block EA #07-08, 9 Engineering Drive 1, 117576, Singapore
*
*Email: [email protected]
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Abstract

We present a calculation of vibrational frequencies of formate on the AuPt(111) surface alloy including full anharmonicity and coupling of all six intramolecular degrees of freedom. This species is a key intermediate in methanol oxidation on this material. We use a modified version of the method of Manzhos and Carrington to compute the spectrum directly from a small number (<10,000) of DFT single-point energies, bypassing the construction of a potential energy surface. This is the first such calculation for a 4-atomic species at a surface. The spectrum is obtained using rectangular collocation and a small basis set of parameterized Hermite functions. The achievable accuracy of the order of several cm-1 corresponds to the typical experimental resolution. Using normal coordinates makes the equations simple and general and easily applicable to other systems. This calculation is doable on a PC. We predict that anharmonicity and coupling lower the fundamental frequencies by dozens of cm-1, which could affect species assignment.

Keywords

catalyticsurface reactioninfrared (IR) spectroscopy
Type
Articles
Information
MRS Online Proceedings Library (OPL) , Volume 1484: Symposium 7A – Advances in Computational Materials Science , 2012 , imrc12-1484-7a-0016
Copyright
Copyright © Materials Research Society 2012 

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