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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10403 - Physical chemistry

Project

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Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2017

Confidentiality

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

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

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Volume of the periodical

19

Issue of the periodical within the volume

27

Country of publishing house

GB - UNITED KINGDOM

Number of pages

7

Pages from-to

17531-17537

UT code for WoS article

000405424100005

EID of the result in the Scopus database

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