Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution
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Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution. / Pedersen, Jacob; Rasmussen, Maria H.; Mikkelsen, Kurt V.
I: Journal of Chemical Theory and Computation, Bind 18, Nr. 12, 2022, s. 7052−7072.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution
AU - Pedersen, Jacob
AU - Rasmussen, Maria H.
AU - Mikkelsen, Kurt V.
PY - 2022
Y1 - 2022
N2 - Dynamical simulations of ultrafast electron transfer reactions are of utmost interest. To allow for energy dissipation directly into an external surrounding environment, a solvent coupling model has been deduced, implemented, and utilized to describe the photoinduced electron transfer dynamics within a model triad system herein. The model is based on Redfield theory, and the environment is represented by harmonic oscillators filled with bosonic quanta. To imitate real solvents, the oscillators have been equipped with frequencies and polarization lifetimes characteristic of the corresponding solvent. The population was found to transfer through the energetically lowest electron transfer route regardless of the medium. The condensed population transfer dynamics were observed to be highly dependent on the solvent parameters. In particular, an increase in the solvent coupling entailed a detainment in the population transfer from the initially prepared diabatic state and a promotion in the population transfer through the other electron transfer route. Two explanations based on the diagonal and off-diagonal matrix elements of the Kohn-Sham Fock matrix, respectively, have been provided. The lifetime of the populated partially charge-separated state was prolonged with increasing solvent polarity, and it was explained in terms of attractive interactions between the solvent's dipole moments and the fragments' charges. The high-frequency vibrational fine-structure in the correlation function was demonstrated to be important for the transfer dynamics, and the importance of dephasing effects in polar solvents was verified and precised to concern the optical polarization the solvents.
AB - Dynamical simulations of ultrafast electron transfer reactions are of utmost interest. To allow for energy dissipation directly into an external surrounding environment, a solvent coupling model has been deduced, implemented, and utilized to describe the photoinduced electron transfer dynamics within a model triad system herein. The model is based on Redfield theory, and the environment is represented by harmonic oscillators filled with bosonic quanta. To imitate real solvents, the oscillators have been equipped with frequencies and polarization lifetimes characteristic of the corresponding solvent. The population was found to transfer through the energetically lowest electron transfer route regardless of the medium. The condensed population transfer dynamics were observed to be highly dependent on the solvent parameters. In particular, an increase in the solvent coupling entailed a detainment in the population transfer from the initially prepared diabatic state and a promotion in the population transfer through the other electron transfer route. Two explanations based on the diagonal and off-diagonal matrix elements of the Kohn-Sham Fock matrix, respectively, have been provided. The lifetime of the populated partially charge-separated state was prolonged with increasing solvent polarity, and it was explained in terms of attractive interactions between the solvent's dipole moments and the fragments' charges. The high-frequency vibrational fine-structure in the correlation function was demonstrated to be important for the transfer dynamics, and the importance of dephasing effects in polar solvents was verified and precised to concern the optical polarization the solvents.
KW - CORRELATED MOLECULAR CALCULATIONS
KW - GAUSSIAN-BASIS SETS
KW - DIELECTRIC RESPONSE
KW - PARA-NITROANILINE
KW - BINARY-MIXTURES
KW - FIELD
KW - TRANSITION
KW - SOLVATION
KW - SYSTEMS
U2 - 10.1021/acs.jctc.2c00538
DO - 10.1021/acs.jctc.2c00538
M3 - Journal article
C2 - 36413807
VL - 18
SP - 7052−7072
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
SN - 1549-9618
IS - 12
ER -
ID: 329436809