Work

Accurate Prediction of Photoinduced Electron Transfer Timescales with Nonadiabatic Microcanonical Rate Theory

Year: 2026

Type: article

Abstract: Photoinduced electron transfer (PET) lies at the heart of energy conversion from light into chemical reactions. It governs a variety of biological processes including DNA damage and repair and biological photosynthesis. Quantifying PET rates and optimizing them is also crucial for selective photoredox catalysis. However, commonly used rate theories break down for PET operating in the strong coupling and nonequilibrium regimes, while excited-state dynamics simulations are computationally demanding and require complex analysis to extract PET times. Here, we employed surface-hopping nonadiabatic excited-state dynamics simulations and statistical rate theories to characterize ultrafast PET in a dimer of stacked adenine nucleobases. We show that the widely used classical Marcus Theory and Fermi's Golden Rule fail to describe ultrafast PET or even reproduce qualitative rate trends. Instead, we propose a chromophore-localized variant of nonadiabatic Rice-Rampsperger-Kassel-Marcus (NA-RRKM) theory, which yields PET timescales that are in excellent agreement with excited-state dynamics simulations.

Source: The Journal of Physical Chemistry Letters

DOI: 10.1021/acs.jpclett.5c03913

Authors: Rafał Szabla, Cristina A. Barboza

Institution: Wrocław University of Science and Technology

Language: English

Topic: Photochemistry and Electron Transfer Studies

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funder: Narodowe Centrum Nauki