Cover Image

Rotational effects on the dissociation dynamics of CHD3 on Pt(111)

Dissociation of methane on metal surfaces is of high practical and fundamental interest. Therefore there is currently a big push aimed at determining the simplest dynamical model that allows the reaction dynamics to be described with quantitative accuracy using quantum dynamics. Using five-dimension...

Full description

Saved in:
Bibliographic Details
Main Authors: Füchsel, Gernot (Author) , Thomas, Phillip S. (Author) , Uyl, Jurriaan den (Author) , Öztürk, Yesim (Author) , Nattino, Francesco (Author) , Meyer, Hans-Dieter (Author) , Kroes, Geert-Jan (Author)
Format: Article (Journal)
Language:English
Published: 23 February 2016
In: Physical chemistry, chemical physics
Year: 2016, Volume: 18, Issue: 11, Pages: 8174-8185
ISSN:1463-9084
DOI:10.1039/C5CP07898A
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C5CP07898A
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2016/cp/c5cp07898a
Get full text
Author Notes:Gernot Füchsel, Phillip S. Thomas, Jurriaan den Uyl, Yesim Öztürk, Francesco Nattino, Hans-Dieter Meyer and Geert-Jan Kroes
Description
Summary:Dissociation of methane on metal surfaces is of high practical and fundamental interest. Therefore there is currently a big push aimed at determining the simplest dynamical model that allows the reaction dynamics to be described with quantitative accuracy using quantum dynamics. Using five-dimensional quantum dynamical and full-dimensional ab initio molecular dynamics calculations, we show that the CD3 umbrella axis of CHD3 must reorient before the molecule reaches the barrier for C-H cleavage to occur in reaction on Pt(111). This rules out the application of the rotationally sudden approximation, as explicitly shown through a comparison with calculations using this approximation. Further, we suggest that the observed umbrella swing should strongly affect the sensitivity of C-H cleavage to the initial alignment of the molecule relative to the surface as found experimentally for closely related systems. We find very large differences in reactivity for molecules pre-excited to different rotational states, particularly if these states are associated with different orientations of the C-H bond.
Item Description:Im Titel ist die Ziffer "3" tiefgestellt
Gesehen am 05.06.2020
Physical Description:Online Resource
ISSN:1463-9084
DOI:10.1039/C5CP07898A

Similar Items