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

2018/06/30 by Dino Novko, D. Novko, Jean Christophe Tremblay +3
Earth and Planetary Sciences · Physics and Astronomy · #Advanced Chemical Physics Studies #Atomic physics #Chemical physics #Coupling (piping) #Electron #Femtosecond #Laser #Laser linewidth #Materials science #Molecular physics #Molecular vibration #Optics #Physics #Raman spectroscopy #Spectroscopy #Spectroscopy and Quantum Chemical Studies #Transient (computer programming) #Ultrafast laser spectroscopy #Ultrashort pulse #cond-mat.mtrl-sci #nanoparticles nucleation surface interactions

paper · pdf · doi:10.1103/physrevlett.122.016806

published as Phys. Rev. Lett. 122, 016806 (2019) · Article as accepted for publication in Physical Review Letters; 5 pages, 2 figures, 1 table

openalex publication_date 2019/01/10 · arxiv created 2019/01/11 · arxiv updated 2019/01/14 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

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.

Citations