Quantum mechanical tunnelling: the missing term to achieve sub-kJ mol−1 barrier heights

Literature Information

Publication Date 2021-04-21
DOI 10.1039/D1CP01275D
Impact Factor 3.676
Authors

Sebastian Kozuch, Tim Schleif, Amir Karton


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Abstract

To predict barrier heights at low temperatures, it is not enough to employ highly accurate electronic structure methods. We discuss the influence of quantum tunnelling on the comparison of experimental and theoretical activation parameters (Ea, ΔH‡, ΔG‡, or ΔS‡), since the slope-based experimental techniques to obtain them completely neglect the tunnelling component. The intramolecular degenerate rearrangement of four fluxional molecules (bullvalene, barbaralane, semibullvalene, and norbornadienylidene) were considered, systems that cover the range between fast deep tunneling and small but significant shallow tunnelling correction. The barriers were computed with the composite W3lite-F12 method at the CCSDT(Q)/CBS level, and the tunnelling contribution with small curvature tunnelling. While at room temperature the effect is small (∼1 kJ mol−1), at low temperatures it can be considerable (in the order of tens of kJ mol−1 at ∼80 K).

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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