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Chemisorbed Molecules under Potential Bias: Detailed Insights from First-Principles Vibrational Spectroscopies

Authors
  • Bonnet, Nicéphore
  • Dabo, Ismaila
  • Marzari, Nicola
Type
Published Article
Journal
Electrochimica Acta
Publisher
Elsevier
Publication Date
Jan 01, 2014
Accepted Date
Dec 23, 2013
Volume
121
Pages
210–214
Identifiers
DOI: 10.1016/j.electacta.2013.12.115
Source
Elsevier
Keywords
License
Unknown

Abstract

The electrochemical factors that control the interaction of a chemisorbed molecule under potential bias are identified by considering the vibrational response of carbon monoxide on a platinum electrode from first principles. Using three complementary approaches to simulate the potential bias, it is shown that the frequency shifts upon electrode bias are electrostatic in nature and give rise to the vibrational Stark effect, in which the first and second-order responses are determined by the dipole moment and the capacitance of the system, respectively. These results are rationalized by examining the central role of electrostatic screening by the metal at the atomic scale.

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