On the temperature dependence of electronically non-adiabatic vibrational energy transfer in molecule-surface collisions

Daniel Matsiev, Zhisheng Li, Russell Cooper, Igor Rahinov, Christof Bartels, Daniel J. Auerbach, Alec M. Wodtke

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

Here we extend a recently introduced state-to-state kinetic model describing single- and multi-quantum vibrational excitation of molecular beams of NO scattering from a Au(111) metal surface. We derive an analytical expression for the rate of electronically non-adiabatic vibrational energy transfer, which is then employed in the analysis of the temperature dependence of the kinetics of direct overtone and two-step sequential energy transfer mechanisms. We show that the Arrhenius surface temperature dependence for vibrational excitation probability reported in many previous studies emerges as a low temperature limit of a more general solution that describes the approach to thermal equilibrium in the limit of infinite interaction time and that the pre-exponential term of the Arrhenius expression can be used not only to distinguish between the direct overtone and sequential mechanisms, but also to deduce their relative contributions. We also apply the analytical expression for the vibrational energy transfer rates introduced in this work to the full kinetic model and obtain an excellent fit to experimental data, the results of which show how to extract numerical values of the molecule-surface coupling strength and its fundamental properties.

Original languageEnglish
Pages (from-to)8153-8162
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number18
DOIs
StatePublished - 21 Apr 2011
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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