Tunneling chemical exchange reaction D + HD → D2 + H in solid HD and D2 at temperatures below 1 K

Literature Information

Publication Date 2016-10-06
DOI 10.1039/C6CP05486B
Impact Factor 3.676
Authors

S. Sheludiakov, J. Ahokas, J. Järvinen, L. Lehtonen, O. Vainio, S. Vasiliev, D. M. Lee, V. V. Khmelenko


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Abstract

We report on a study of the exchange tunneling reaction D + HD → D2 + H in a pure solid HD matrix and in a D2 matrix with a 0.23% HD admixture at temperatures between 130 mK and 1.5 K. We found that the exchange reaction rates, kexHD ∼ 3 × 10−27 cm3 s−1 in the pure HD matrix, and kexD2 = 9(4) × 10−28 cm3 s−1 in the D2 matrix, are nearly independent of temperature within this range. This confirms the quantum tunnelling nature of these reactions, and their ability to proceed at temperatures down to absolute zero. Based on these observations we concluded that exchange tunneling reaction H + H2 → H2 + H should also proceed in a H2 matrix at the lowest temperatures. On the other hand, the recombination of H atoms in solid H2 and D atoms in solid D2 is substantially suppressed at the lowest temperatures as a result of a decreased probability of resonant tunneling of atoms when they approach each other.

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Source Journal

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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