Solvation Effects Alter the Photochemistry of 2-Thiocytosine

TL;DR

This study uses advanced quantum-chemical simulations to reveal how water molecules influence the excited-state dynamics and nonradiative decay pathways of 2-thiocytosine, highlighting a novel water-chromophore electron transfer process.

Contribution

It introduces the first evidence of water-chromophore electron transfer in the triplet state of 2-thiocytosine, expanding understanding of solvation effects on its photochemistry.

Findings

Water molecules enable electron transfer to the thiocarbonyl group.

Water-chromophore electron transfer occurs in the triplet state, previously unconsidered.

This process may lead to formation of hydroxyl radicals and influence photohydration reactions.

Abstract

Radiationless deactivation channels of 2-thiocytosine in aqueous environment are revisited by means of quantum-chemical simulations of excited-state absorption spectra, and investigations of potential energy surfaces of the chromophore clustered with two water molecules using the algebraic diagrammatic construction method to the second-order (ADC(2)), and multireference configuration interaction with single and double excitations (MR-CISD) methods. We argue that interactions of explicit water molecules with thiocarbonyl group might enable water-chromophore electron transfer (WCET) which leads to formation of intersystem crossing that was not considered previously. This is the first example of a WCET process occurring in the triplet manifold of electronic states. This phenomenon might explain nonradiative decay of the triplet state population observed in thiopyrimidines in the absence of molecular oxygen. According to our calculations this WCET process might also entail a subsequent, virtually barrierless, electron-driven proton transfer (EDPT) resulting in the formation of hydroxyl radical which could further participate in photohydration or deamination reactions.