TY - JOUR
T1 - Photoisomerization-coupled electron transfer
AU - Sowa, Jakub K.
AU - Weiss, Emily A.
AU - Seideman, Tamar
N1 - Funding Information:
The authors thank Roel Tempelaar for comments on the manuscript. This work was supported by the National Science Foundation’s MRSEC program (Grant No. DMR-1720139) at the Materials Research Center of Northwestern University. This research was also supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology.
PY - 2020/7/21
Y1 - 2020/7/21
N2 - Photochromic molecular structures constitute a unique platform for constructing molecular switches, sensors, and memory devices. One of their most promising applications is as light-switchable electron acceptor or donor units. Here, we investigate a previously unexplored process that we postulate may occur in such systems: an ultrafast electron transfer triggered by a simultaneous photoisomerization of the donor or the acceptor moiety. We propose a theoretical model for this phenomenon and, with the aid of density functional theory calculations, apply it to the case of a dihydropyrene-type photochromic molecular donor. By considering the wavepacket dynamics and the photoisomerization yield, we show that the two processes involved, electron transfer and photoisomerization, are in general inseparable and need to be treated in a unified manner. We finish by discussing how the efficiency of photoisomerization-coupled electron transfer can be controlled experimentally.
AB - Photochromic molecular structures constitute a unique platform for constructing molecular switches, sensors, and memory devices. One of their most promising applications is as light-switchable electron acceptor or donor units. Here, we investigate a previously unexplored process that we postulate may occur in such systems: an ultrafast electron transfer triggered by a simultaneous photoisomerization of the donor or the acceptor moiety. We propose a theoretical model for this phenomenon and, with the aid of density functional theory calculations, apply it to the case of a dihydropyrene-type photochromic molecular donor. By considering the wavepacket dynamics and the photoisomerization yield, we show that the two processes involved, electron transfer and photoisomerization, are in general inseparable and need to be treated in a unified manner. We finish by discussing how the efficiency of photoisomerization-coupled electron transfer can be controlled experimentally.
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U2 - 10.1063/5.0013468
DO - 10.1063/5.0013468
M3 - Article
C2 - 32716166
AN - SCOPUS:85088318011
VL - 153
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 3
M1 - 034301
ER -