Conformational dynamics modulating electron transfer
Abstract
Diffusional dynamics of the donor–acceptor distance are responsible for the appearance of a new time scale of diffusion over the distance of electronic tunneling in electron-transfer reactions. The distance dynamics compete with the medium polarization dynamics in the dynamics-controlled electron-transfer kinetics. The pre-exponential factor of the electron-transfer rate constant switches, at the crossover distance, between a distance-independent, dynamics-controlled plateau and exponential distance decay. The crossover between two regimes is controlled by an effective relaxation time slowed down by a factor exponentially depending on the variance of the donor–acceptor displacement. Flexible donor–acceptor complexes must show a greater tendency for dynamics-controlled electron transfer. Energy chains based on electron transport are best designed by placing the redox cofactors near the crossover distance.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Sep 06, 2022
- Source ID
- 10.1063/5.0102707
Entities
People
- Dmitry V. Matyushov
Organizations
- Arizona State University
- Army Research Office
- National Science Foundation