Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics
Entity
UAM. Departamento de QuímicaPublisher
American Institute of PhysicsDate
2012-08-14Citation
10.1063/1.4742907
Journal of Chemical Physic 137.6 (2012): 064707
ISSN
0021-9606 (print); 1089-7690 (online)DOI
10.1063/1.4742907Funded by
This work has been financially supported by the DGI (Project Nos. FIS2010-15127 and FIS2010-19609-C02-02), the CAM (Project No. 2009/MAT1726), the Basque Dpto. de Educación, Universidades e Investigación, and the UPV/EHU (Project No. IT-366-07)Project
Comunidad de Madrid. S2009/MAT-1726/NANOBIOMAGNETEditor's Version
http://dx.doi.org/10.1063/1.4742907Subjects
QuímicaNote
The following article appeared in Journal of Chemical Physic 137.6 (2012): 064707 and may be found at http://scitation.aip.org/content/aip/journal/jcp/137/6/10.1063/1.4742907Rights
© 2012 American Institute of PhysicsAbstract
We have studied survival and rotational excitation probabilities of H2(vi = 1, Ji = 1) and D2(vi = 1, Ji = 2) upon scattering from Cu(111) using six-dimensional (6D) adiabatic (quantum and quasi-classical) and non-adiabatic (quasi-classical) dynamics. Non-adiabatic dynamics, based on a friction model, has been used to analyze the role of electron-hole pair excitations. Comparison between adiabatic and non-adiabatic calculations reveals a smaller influence of non-adiabatic effects on the energy dependence of the vibrational deexcitation mechanism than previously suggested by low-dimensional dynamics calculations. Specifically, we show that 6D adiabatic dynamics can account for the increase of vibrational deexcitation as a function of the incidence energy, as well as for the isotope effect observed experimentally in the energy dependence for H2(D2)/Cu(100). Furthermore, a detailed analysis, based on classical trajectories, reveals that in trajectories leading to vibrational deexcitation, the minimum classical turning point is close to the top site, reflecting the multidimensionally of this mechanism. On this site, the reaction path curvature favors vibrational inelastic scattering. Finally, we show that the probability for a molecule to get close to the top site is higher for H2 than for D2, which explains the isotope effect found experimentally
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Google Scholar:Muzas, Alberto S.
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Juaristi, J. Iñaki
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Alducin, Maite
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Kroes, Geert Jan
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Díaz Oliva, Cristina
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Muiño, R. Díez
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