Ultrafast Transient Dynamics of Adsorbates on Surfaces Deciphered: The Case of CO on Cu(100)

Time-resolved vibrational spectroscopy constitutes an invaluable experimental tool for monitoring hot-carrier-induced surface reactions. However, the absence of a full understanding of the precise microscopic mechanisms causing the transient spectral changes has limited its applicability. Here we in...

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Bibliographic Details
Published in:Physical review letters 2019-01, Vol.122 (1), p.016806-016806, Article 016806
Main Authors: Novko, D, Tremblay, J C, Alducin, M, Juaristi, J I
Format: Article
Language:English
Subjects:
Adsorbates
Chemical Sciences
Coupling
Femtosecond pulses
First principles
Holes (electron deficiencies)
or physical chemistry
Physics
Quantum Physics
Surface reactions
Theoretical and
Vibration monitoring
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Summary:Time-resolved vibrational spectroscopy constitutes an invaluable experimental tool for monitoring hot-carrier-induced surface reactions. However, the absence of a full understanding of the precise microscopic mechanisms causing the transient spectral changes has limited its applicability. Here we introduce a robust first-principles theoretical framework that successfully explains both the nonthermal frequency and linewidth changes of the CO internal stretch mode on Cu(100) induced by femtosecond laser pulses. Two distinct processes engender the changes: electron-hole pair excitations underlie the nonthermal frequency shifts, while electron-mediated vibrational mode coupling gives rise to linewidth changes. Furthermore, the origin and precise sequence of coupling events are finally identified.
ISSN:0031-9007
1079-7114
DOI:10.1103/physrevlett.122.016806