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Title: Computing intramolecular charge and energy transfer rates using optimal modes

Abstract

In our recent work [X. Yang and E. R. Bittner, J. Phys. Chem. A 118, 5196 (2014)], we showed how to construct a reduced set of nuclear motions that capture the coupling between electronic and nuclear degrees of freedom over the course of an electronic transition. We construct these modes, referred to as “Lanczos modes,” by applying a search algorithm to find linear combinations of vibrational normal modes that optimize the electronic/nuclear coupling operator. Here, we analyze the irreducible representations of the dominant contributions of these modes and find that for the cases considered here, these belong to totally symmetric irreducible representations of the donor and acceptor moieties. Upon investigating the molecular geometry changes following the transition, we propose that the electronic transition process can be broken into two steps, in the agreement of Born-Oppenheimer approximation: a fast excitation transfer occurs, facilitated by the “primary Lanczos mode,” followed by slow nuclear relaxation on the final electronic diabatic surface.

Authors:
Publication Date:
OSTI Identifier:
22490833
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 24; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BORN-OPPENHEIMER APPROXIMATION; COUPLING; DEGREES OF FREEDOM; ENERGY TRANSFER; EXCITATION; IRREDUCIBLE REPRESENTATIONS; SURFACES

Citation Formats

Yang, Xunmo, and Bittner, Eric R., E-mail: bittner@uh.edu. Computing intramolecular charge and energy transfer rates using optimal modes. United States: N. p., 2015. Web. doi:10.1063/1.4923191.
Yang, Xunmo, & Bittner, Eric R., E-mail: bittner@uh.edu. Computing intramolecular charge and energy transfer rates using optimal modes. United States. https://doi.org/10.1063/1.4923191
Yang, Xunmo, and Bittner, Eric R., E-mail: bittner@uh.edu. 2015. "Computing intramolecular charge and energy transfer rates using optimal modes". United States. https://doi.org/10.1063/1.4923191.
@article{osti_22490833,
title = {Computing intramolecular charge and energy transfer rates using optimal modes},
author = {Yang, Xunmo and Bittner, Eric R., E-mail: bittner@uh.edu},
abstractNote = {In our recent work [X. Yang and E. R. Bittner, J. Phys. Chem. A 118, 5196 (2014)], we showed how to construct a reduced set of nuclear motions that capture the coupling between electronic and nuclear degrees of freedom over the course of an electronic transition. We construct these modes, referred to as “Lanczos modes,” by applying a search algorithm to find linear combinations of vibrational normal modes that optimize the electronic/nuclear coupling operator. Here, we analyze the irreducible representations of the dominant contributions of these modes and find that for the cases considered here, these belong to totally symmetric irreducible representations of the donor and acceptor moieties. Upon investigating the molecular geometry changes following the transition, we propose that the electronic transition process can be broken into two steps, in the agreement of Born-Oppenheimer approximation: a fast excitation transfer occurs, facilitated by the “primary Lanczos mode,” followed by slow nuclear relaxation on the final electronic diabatic surface.},
doi = {10.1063/1.4923191},
url = {https://www.osti.gov/biblio/22490833}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 24,
volume = 142,
place = {United States},
year = {Sun Jun 28 00:00:00 EDT 2015},
month = {Sun Jun 28 00:00:00 EDT 2015}
}