Double proton transfer reactions at the transition from a concerted to a stepwise mechanism: a comparative ab initio study

Literature Information

Publication Date 2005-01-10
DOI 10.1039/B415528A
Impact Factor 3.676
Authors

Stefan Schweiger, Bernd Hartke, Guntram Rauhut


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Abstract

The double proton transfer reactions between some substituted pyrazoles and guanidine were studied by ab initio calculations up to the CCSD(T) level. In contrast to standard textbook reactions, two of the systems show broad plateaus of almost constant energy along the minimum energy path (MEP) instead of well localized transition states. The impact of zero point vibrational energy (ZPE) corrections on the energy profiles are discussed in detail. Analyses based on the reaction path Hamiltonian (RPH) were used to gain further insight into the properties of the reaction paths. For one system RPH dynamics simulations were used to determine the life time on top of the plateau and the conversion coefficient entering into the overall rate constant. One dimensional (1D) tunneling effects were studied along the MEPs and a linear reaction path.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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