Beyer, Adrian N., Richardson, Jeremy O., Knowles, Peter J.  ORCID: https://orcid.org/0000-0003-4657-6331, Rommel, Judith and Althorpe, Stuart C.
2016.
Quantum tunneling rates of gas-phase reactions from on-the-fly instanton calculations.
Journal of Physical Chemistry Letters
7
(21)
, pp. 4374-4379.
10.1021/acs.jpclett.6b02115
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Abstract
The instanton method obtains approximate tunneling rates from the minimum-action path (known as the instanton) linking reactants to the products at a given temperature. An efficient way to find the instanton is to search for saddle-points on the ring-polymer potential surface, which is obtained by expressing the quantum Boltzmann operator as a discrete path-integral. Here we report a practical implementation of this ring-polymer form of instanton theory into the Molpro electronic-structure package, which allows the rates to be computed on-the-fly, without the need for a fitted analytic potential-energy surface. As a test case, we compute tunneling rates for the benchmark H + CH4 reaction, showing how the efficiency of the instanton method allows the user systematically to converge the tunneling rate with respect to the level of electronic-structure theory.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Professional Services > Advanced Research Computing @ Cardiff (ARCCA) Schools > Chemistry |
| Publisher: | American Chemical Society |
| ISSN: | 1948-7185 |
| Funders: | EPSRC |
| Date of First Compliant Deposit: | 29 November 2016 |
| Date of Acceptance: | 19 October 2016 |
| Last Modified: | 04 May 2023 06:31 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/96488 |
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