Detailed study of the direct numerical observation of the Kramers turnover in the LiNC⇌LiCN isomerization rate
Entity
UAM. Departamento de QuímicaPublisher
American Institute of PhysicsDate
2012-11-27Citation
10.1063/1.4766257
Journal of Chemical Physics 137.20 (2012): 204301
ISSN
0021-9606 (print); 1089-7690 (online)DOI
10.1063/1.4766257Funded by
This work has been supported by the Spanish MINECO under projects MTM2009-14621 and ICMAT Severo Ochoa SEV-2011-0087. It also has been partially supported by the U.S. National Science Foundation under Grant No. CHE-1112067. Travel between partners was partially supported through the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme FP7/2007-2013/ under REA Grant Agreement No. 294974Project
info:eu-repo/grantAgreement/EC/FP7/294974Editor's Version
http://dx.doi.org/10.1063/1.4766257Subjects
QuímicaNote
The following article appeared in Journal of Chemical Physics 137.20 (2012): 204301 and may be found at http://scitation.aip.org/content/aip/journal/jcp/137/20/10.1063/1.4766257Rights
© 2012 American Institute of PhysicsAbstract
According to Kramers, rates of molecular process are expected to follow a rise and fall from low friction (at little to no interaction with the environment) to high friction (at typical liquid densities and above). This so-called Kramers turnover was recently observed and delineated in the case of the LiNC⇌LiCN isomerization reaction in the presence of an argon bath [P. García-Müller, R. Hernandez, R. M. Benito, and F. Borondo, Phys. Rev. Lett. 101, 178302 (2008)]. The rates were obtained using direct molecular dynamics of an all-atom representation and the Langevin dynamics of a projected representation. We now provide further evidence that the forward and backward rates are indeed exhibiting the turnover. The rates are also seen to agree remarkably well with the Pollak-Grabert-Hänggi rate formulas in regimes satisfying the theory underlying assumptions. At higher temperatures, when the theory is expected to fail, the solvated LiCN isomerization continues to exhibit activated dynamics following the turnover
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Google Scholar:Benito, Rosa María
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Borondo, Florentino
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García Müller, P. L
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Hernandez, Rigoberto
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