The Library
Dissipative tunneling rates through the incorporation of first-principles electronic friction in instanton rate theory. I. Theory
Tools
Litman, Y., Pós, E. S., Box, C. L., Martinazzo, R., Maurer, R. J. and Rossi, M. (2022) Dissipative tunneling rates through the incorporation of first-principles electronic friction in instanton rate theory. I. Theory. The Journal of Chemical Physics, 156 (19). 194106. doi:10.1063/5.0088399 ISSN 0021-9606.
|
PDF
WRAP-Dissipative-tunneling-rates-through-the-incorporation-of-first-principles-electronic-friction-in-instanton-rate-theory-I-Theory-Box-22.pdf - Published Version - Requires a PDF viewer. Available under License Creative Commons Attribution 4.0. Download (5Mb) | Preview |
Official URL: http://dx.doi.org/10.1063/5.0088399
Abstract
Reactions involving adsorbates on metallic surfaces and impurities in bulk metals are ubiquitous in a wide range of technological applications. The theoretical modeling of such reactions presents a formidable challenge for theory because nuclear quantum effects (NQEs) can play a prominent role and the coupling of the atomic motion with the electrons in the metal gives rise to important non-adiabatic effects (NAEs) that alter atomic dynamics. In this work, we derive a theoretical framework that captures both NQEs and NAEs and, due to its high efficiency, can be applied to first-principles calculations of reaction rates in high-dimensional realistic systems. More specifically, we develop a method that we coin ring polymer instanton with explicit friction (RPI-EF), starting from the ring polymer instanton formalism applied to a system–bath model. We derive general equations that incorporate the spatial and frequency dependence of the friction tensor and then combine this method with the ab initio electronic friction formalism for the calculation of thermal reaction rates. We show that the connection between RPI-EF and the form of the electronic friction tensor presented in this work does not require any further approximations, and it is expected to be valid as long as the approximations of both underlying theories remain valid.
Item Type: | Journal Article | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Subjects: | Q Science > QC Physics T Technology > TA Engineering (General). Civil engineering (General) |
|||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Chemistry > Computational and Theoretical Chemistry Centre |
|||||||||||||||
Library of Congress Subject Headings (LCSH): | Metals -- Surfaces , Quantum theory, Instantons , Born-Oppenheimer approximation , Molecular dynamics, Friction | |||||||||||||||
Journal or Publication Title: | The Journal of Chemical Physics | |||||||||||||||
Publisher: | American Institute of Physics | |||||||||||||||
ISSN: | 0021-9606 | |||||||||||||||
Official Date: | 16 May 2022 | |||||||||||||||
Dates: |
|
|||||||||||||||
Volume: | 156 | |||||||||||||||
Number: | 19 | |||||||||||||||
Number of Pages: | 11 | |||||||||||||||
Article Number: | 194106 | |||||||||||||||
DOI: | 10.1063/5.0088399 | |||||||||||||||
Status: | Peer Reviewed | |||||||||||||||
Publication Status: | Published | |||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||
Date of first compliant deposit: | 28 June 2022 | |||||||||||||||
Date of first compliant Open Access: | 29 June 2022 | |||||||||||||||
RIOXX Funder/Project Grant: |
|
Request changes or add full text files to a record
Repository staff actions (login required)
View Item |
Downloads
Downloads per month over past year