Water-chromophore electron transfer determines the photochemistry of cytosine and cytidine

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68081707%3A_____%2F17%3A00485637" target="_blank" >RIV/68081707:_____/17:00485637 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1039/c7cp02635h" target="_blank" >http://dx.doi.org/10.1039/c7cp02635h</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c7cp02635h" target="_blank" >10.1039/c7cp02635h</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Water-chromophore electron transfer determines the photochemistry of cytosine and cytidine

Popis výsledku v původním jazyce

Many of the UV-induced phenomena observed experimentally for aqueous cytidine were lacking the mechanistic interpretation for decades. These processes include the substantial population of the puzzling long-lived dark state, photohydration, cytidine to uridine conversion and oxazolidinone formation. Here, we present quantumchemical simulations of excited-state spectra and potential energy surfaces of N1-methylcytosine clustered with two water molecules using the second-order approximate coupled cluster (CC2), complete active space with second-order perturbation theory (CASPT2), and multireference configuration interaction with single and double excitation (MR-CISD) methods. We argue that the assignment of the long-lived dark state to a singlet n pi* excitation involving water-chromophore electron transfer might serve as an explanation for the numerous experimental observations. While our simulated spectra for the n pi*(CT) state are in excellent agreement with experimentally acquired data, the electron-driven proton transfer process occurring on the n pi*(CT) surface may initiate the subsequent damage in the vibrationally hot ground state of the chromophore.

Název v anglickém jazyce

Water-chromophore electron transfer determines the photochemistry of cytosine and cytidine

Popis výsledku anglicky

Many of the UV-induced phenomena observed experimentally for aqueous cytidine were lacking the mechanistic interpretation for decades. These processes include the substantial population of the puzzling long-lived dark state, photohydration, cytidine to uridine conversion and oxazolidinone formation. Here, we present quantumchemical simulations of excited-state spectra and potential energy surfaces of N1-methylcytosine clustered with two water molecules using the second-order approximate coupled cluster (CC2), complete active space with second-order perturbation theory (CASPT2), and multireference configuration interaction with single and double excitation (MR-CISD) methods. We argue that the assignment of the long-lived dark state to a singlet n pi* excitation involving water-chromophore electron transfer might serve as an explanation for the numerous experimental observations. While our simulated spectra for the n pi*(CT) state are in excellent agreement with experimentally acquired data, the electron-driven proton transfer process occurring on the n pi*(CT) surface may initiate the subsequent damage in the vibrationally hot ground state of the chromophore.

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

2017

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

19

Číslo periodika v rámci svazku

27

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

7

Strana od-do

17531-17537

Kód UT WoS článku

000405424100005

EID výsledku v databázi Scopus

—