Semiclassical reaction rate constant of non-adiabatic system by means of initial value representation
Source abstract
Abstract
We applied the semiclassical initial value representation (SC-IVR) method with the classical electron analog to deal with electronically non-adiabatic reactive barriers and calculated the thermal reaction rate constant. The symmetric form of the flux–flux correlation function is used, and the matrix element of the Boltzmannized flux operator is derived using imaginary-time path integral techniques. This combined use of non-adiabatic SC-IVR and non-adiabatic path-integral sampling (NA-IVR&PI) is beyond the treatment of mean-field, and we analyze its performance in comparison with some existing mean-field methods for different scenarios of potential energy surface. We found a systematically better performance. One exception is the deep tunneling regime, where the mean-field ring-polymer instanton is superior. In the golden rule limit, where all these mean-field methods break down, the significant advantage of NA-IVR&PI is shown by using the electronic states for description of the dividing surface.
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Research context
OpenAlex topics: Advanced Chemical Physics Studies · Spectroscopy and Quantum Chemical Studies · Quantum, superfluid, helium dynamics
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
State Key Laboratory for Artificial Microstructure and Mesoscopic Physics, Frontier Science Center for Nano-optoelectronics and School of Physics, Peking University 1 , Beijing 100871, People’s Republic of China
Interdisciplinary Institute of Light-Element Quantum Materials, Research Center for Light-Elemt Advanced Materials, and Collaborative Innovation Center of Quantum Matter, Peking University 2 , Beijing 100871, People’s Republic of China
Peking University Yangtze Delta Institute of Optoelectronics 3 , Nantong, Jiangsu 226010, People’s Republic of China
Funding
National Natural Science Foundation of China · National Basic Research Programs of China · Natural Science Foundation of Beijing Municipality · Strategic Priority Research Program of the Chinese Academy of Sciences
References (48)
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