Hydrogen exchange in formic acid dimer: tunnelling above the barrier

Literature Information

Publication Date 2010-05-13
DOI 10.1039/C001253J
Impact Factor 3.676
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Abstract

The Raman spectrum of formic acid dimer in the OH stretch fundamental range is analysed in terms of a fully coupled vibrational Hamiltonian for the seven most important in-plane degrees of freedom involved in the hydrogen exchange process. The Raman spectrum calculated with potential and polarizability functions obtained from density functional theory reproduces the observed band structure. Wavepacket calculations reveal a remarkably slow hydrogen exchange on the timescale of several ps even at excess energies in the range of 10–15 kJ mol−1. The highly non-statistical process is shown to proceed via adiabatic tunnelling even if excess energy is deposited directly into the reaction coordinate.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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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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