Abstract
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.
| Original language | English (US) |
|---|---|
| Article number | 034301 |
| Journal | Journal of Chemical Physics |
| Volume | 153 |
| Issue number | 3 |
| DOIs | |
| State | Published - Jul 21 2020 |
Funding
The authors thank Roel Tempelaar for comments on the manuscript. This work was supported by the National Science Foundation\u2019s 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.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry