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Issue 13, 2004
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Analysis and dynamics of unusual double proton transfer reactions based on the reaction path Hamiltonian

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Abstract

The double proton transfer reactions of the model base pair systems pyrazoleguanidine and pyrazolecyanoguanidine were investigated at the MP2/[aug]-cc-pVDZ and CCSD(T)/[aug]-cc-pVDZ levels of theory. The dynamics of these two systems were studied within the reaction path Hamiltonian (RPH) formalism including the most important curvature coupling elements and all mode-mode couplings. In contrast to the proton transfer of the pyrazole–cyanoguanidine complex, the pyrazole–guanidine system is an example for a plateau reaction with a structureless transition region instead of a well localized transition state. We discuss the effects of the different forms of the minimum energy paths (MEP), of the curvature and of the couplings on the probability of trajectory reflections and thus on the conversion coefficient, entering into the overall rate constant. A comparison with variational transition state theory (VTST) is provided. Furthermore, the effects of different isotopes at various temperatures are presented.

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Publication details

The article was received on 18 Feb 2004, accepted on 02 Apr 2004 and first published on 07 May 2004


Article type: Paper
DOI: 10.1039/B402534B
Phys. Chem. Chem. Phys., 2004,6, 3341-3349

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    Analysis and dynamics of unusual double proton transfer reactions based on the reaction path Hamiltonian

    S. Schweiger, B. Hartke and G. Rauhut, Phys. Chem. Chem. Phys., 2004, 6, 3341
    DOI: 10.1039/B402534B

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