Nonequilibrium vibrational population and donor-acceptor vibrations affecting rates of radiationless transitions

Matyushov, Dmitry V.

doi:10.1063/1.5082970

Title: Nonequilibrium vibrational population and donor-acceptor vibrations affecting rates of radiationless transitions

Journal Article · 21 February 2019 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5082970 · OSTI ID:1493330

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Arizona State Univ., Tempe, AZ (United States). Dept. of of Physics and School of Molecular Sciences; Office of Basic Energy Sciences

Here, an analytical theory is developed for radiationless transitions in molecules characterized by nonequilibrium populations of their vibrational modes. Several changes to the standard transition-state framework follow from nonequilibrium conditions: (i) non-Arrhenius kinetics, (ii) the violation of the fluctuation-dissipation theorem (FDT), and (iii) the breakdown of the detailed balance. The violation of the FDT is reflected in the breakdown of relations between the first (Stokes shift) and second (inhomogeneous band-width) spectral moments, and of similar relations between reorganization parameters for radiationless transitions. The detailed balance between the forward and backward rates is not maintained, requiring a lower effective free energy of the reaction relative to the thermodynamic limit. Lastly, the model suggests that strong control of radiationless transitions can be achieved if a nonequilibrium population of vibrations modulating the donor-acceptor distance is produced.

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Research Organization:: Arizona State Univ., Tempe, AZ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0015641

OSTI ID:: 1493330

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 150; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Nonequilibrium vibrational population and donor-acceptor vibrations affecting rates of radiationless transitions

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References (58)

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