An improved path-integral method for golden-rule rates
We present a simple method for the calculation of reaction rates in the Fermi golden-rule limit, which accurately captures the effects of tunneling and zero-point energy. The method is based on a modification of the recently proposed golden-rule quantum transition state theory (GR-QTST) of Thapa, Fa...
| Main Authors: | , |
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| Format: | Journal article |
| Language: | English |
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American Institute of Physics
2020
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| _version_ | 1826284516471209984 |
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| author | Lawrence, JE Manolopoulos, DE |
| author_facet | Lawrence, JE Manolopoulos, DE |
| author_sort | Lawrence, JE |
| collection | OXFORD |
| description | We present a simple method for the calculation of reaction rates in the Fermi golden-rule limit, which accurately captures the effects of tunneling and zero-point energy. The method is based on a modification of the recently proposed golden-rule quantum transition state theory (GR-QTST) of Thapa, Fang, and Richardson [J. Chem. Phys. 150, 104107 (2019)]. While GR-QTST is not size consistent, leading to the possibility of unbounded errors in the rate, our modified method has no such issue and so can be reliably applied to condensed phase systems. Both methods involve path-integral sampling in a constrained ensemble; the two methods differ, however, in the choice of constraint functional. We demonstrate numerically that our modified method is as accurate as GR-QTST for the one-dimensional model considered by Thapa and co-workers. We then study a multidimensional spin-boson model, for which our method accurately predicts the true quantum rate, while GR-QTST breaks down with an increasing number of boson modes in the discretization of the spectral density. Our method is able to accurately predict reaction rates in the Marcus inverted regime without the need for the analytic continuation required by Wolynes theory. |
| first_indexed | 2024-03-07T01:15:01Z |
| format | Journal article |
| id | oxford-uuid:8e5c2e82-b248-4ee3-bfac-2329d6ffa015 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T01:15:01Z |
| publishDate | 2020 |
| publisher | American Institute of Physics |
| record_format | dspace |
| spelling | oxford-uuid:8e5c2e82-b248-4ee3-bfac-2329d6ffa0152022-03-26T22:57:14ZAn improved path-integral method for golden-rule ratesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:8e5c2e82-b248-4ee3-bfac-2329d6ffa015EnglishSymplectic ElementsAmerican Institute of Physics2020Lawrence, JEManolopoulos, DEWe present a simple method for the calculation of reaction rates in the Fermi golden-rule limit, which accurately captures the effects of tunneling and zero-point energy. The method is based on a modification of the recently proposed golden-rule quantum transition state theory (GR-QTST) of Thapa, Fang, and Richardson [J. Chem. Phys. 150, 104107 (2019)]. While GR-QTST is not size consistent, leading to the possibility of unbounded errors in the rate, our modified method has no such issue and so can be reliably applied to condensed phase systems. Both methods involve path-integral sampling in a constrained ensemble; the two methods differ, however, in the choice of constraint functional. We demonstrate numerically that our modified method is as accurate as GR-QTST for the one-dimensional model considered by Thapa and co-workers. We then study a multidimensional spin-boson model, for which our method accurately predicts the true quantum rate, while GR-QTST breaks down with an increasing number of boson modes in the discretization of the spectral density. Our method is able to accurately predict reaction rates in the Marcus inverted regime without the need for the analytic continuation required by Wolynes theory. |
| spellingShingle | Lawrence, JE Manolopoulos, DE An improved path-integral method for golden-rule rates |
| title | An improved path-integral method for golden-rule rates |
| title_full | An improved path-integral method for golden-rule rates |
| title_fullStr | An improved path-integral method for golden-rule rates |
| title_full_unstemmed | An improved path-integral method for golden-rule rates |
| title_short | An improved path-integral method for golden-rule rates |
| title_sort | improved path integral method for golden rule rates |
| work_keys_str_mv | AT lawrenceje animprovedpathintegralmethodforgoldenrulerates AT manolopoulosde animprovedpathintegralmethodforgoldenrulerates AT lawrenceje improvedpathintegralmethodforgoldenrulerates AT manolopoulosde improvedpathintegralmethodforgoldenrulerates |