Solvation effects alter the photochemistry of 2-thiocytosine

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68081707%3A_____%2F18%3A00501670" target="_blank" >RIV/68081707:_____/18:00501670 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1016/j.chemphys.2018.06.016" target="_blank" >http://dx.doi.org/10.1016/j.chemphys.2018.06.016</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.chemphys.2018.06.016" target="_blank" >10.1016/j.chemphys.2018.06.016</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Solvation effects alter the photochemistry of 2-thiocytosine

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Solvation effects alter the photochemistry of 2-thiocytosine

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemical Physics

ISSN

0301-0104

e-ISSN

—

Svazek periodika

515

Číslo periodika v rámci svazku

NOV 14 2018

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

7

Strana od-do

502-508

Kód UT WoS článku

000454412800055

EID výsledku v databázi Scopus

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