Chemisorbed molecules under potential bias: Detailed insights from first-principles vibrational spectroscopies

Nicéphore Bonnet, Ismaila Dabo, Nicola Marzari

Research output: Contribution to journalArticle

10 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)210-214
Number of pages5
JournalElectrochimica Acta
Volume121
DOIs
StatePublished - Mar 1 2014

Fingerprint

Vibrational spectroscopy
Electrostatics
Stark effect
Electrodes
Molecules
Dipole moment
Carbon Monoxide
Platinum
Carbon monoxide
Screening
Capacitance
Metals

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Electrochemistry

Cite this

@article{9f17f270f21548379cb9da857eda8d89,
title = "Chemisorbed molecules under potential bias: Detailed insights from first-principles vibrational spectroscopies",
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.",
author = "Nic{\'e}phore Bonnet and Ismaila Dabo and Nicola Marzari",
year = "2014",
month = "3",
day = "1",
doi = "10.1016/j.electacta.2013.12.115",
language = "English (US)",
volume = "121",
pages = "210--214",
journal = "Electrochimica Acta",
issn = "0013-4686",
publisher = "Elsevier Limited",

}

Chemisorbed molecules under potential bias : Detailed insights from first-principles vibrational spectroscopies. / Bonnet, Nicéphore; Dabo, Ismaila; Marzari, Nicola.

In: Electrochimica Acta, Vol. 121, 01.03.2014, p. 210-214.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chemisorbed molecules under potential bias

T2 - Detailed insights from first-principles vibrational spectroscopies

AU - Bonnet, Nicéphore

AU - Dabo, Ismaila

AU - Marzari, Nicola

PY - 2014/3/1

Y1 - 2014/3/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84892749861&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84892749861&partnerID=8YFLogxK

U2 - 10.1016/j.electacta.2013.12.115

DO - 10.1016/j.electacta.2013.12.115

M3 - Article

AN - SCOPUS:84892749861

VL - 121

SP - 210

EP - 214

JO - Electrochimica Acta

JF - Electrochimica Acta

SN - 0013-4686

ER -