Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F14%3A00075641" target="_blank" >RIV/00216224:14740/14:00075641 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/68081707:_____/14:00427972

Výsledek na webu

<a href="http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf" target="_blank" >http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201304224" target="_blank" >10.1002/chem.201304224</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases

Popis výsledku v původním jazyce

The photoinduced isomerization of diaminomaleonitrile (DAMN) to diaminofumaronitrile (DAFN) was suggested to play a key role in the prebiotically plausible formation of purine nucleobases and nucleotides. In this work we analyze two competitive photoisomerization mechanisms on the basis of state-of-the-art quantum-chemical calculations. Even though it was suggested that this process might occur on the triplet potential-energy surface, our results indicate that the singlet reaction channel should not bedisregarded either. In fact, the peaked topography of the S-1/S-0 conical intersection suggests that the deexcitation should most likely occur on a sub-picosecond timescale and the singlet photoisomerization mechanism might effectively compete even witha very efficient intersystem crossing. Such a scenario is further supported by the relatively small spin-orbit coupling of the S-1 and T-2 states in the Franck-Condon region, which does not indicate a very effective triplet bypass for thi

Název v anglickém jazyce

Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases

Popis výsledku anglicky

The photoinduced isomerization of diaminomaleonitrile (DAMN) to diaminofumaronitrile (DAFN) was suggested to play a key role in the prebiotically plausible formation of purine nucleobases and nucleotides. In this work we analyze two competitive photoisomerization mechanisms on the basis of state-of-the-art quantum-chemical calculations. Even though it was suggested that this process might occur on the triplet potential-energy surface, our results indicate that the singlet reaction channel should not bedisregarded either. In fact, the peaked topography of the S-1/S-0 conical intersection suggests that the deexcitation should most likely occur on a sub-picosecond timescale and the singlet photoisomerization mechanism might effectively compete even witha very efficient intersystem crossing. Such a scenario is further supported by the relatively small spin-orbit coupling of the S-1 and T-2 states in the Franck-Condon region, which does not indicate a very effective triplet bypass for thi

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2014

Kód důvěrnosti údajů

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

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

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Svazek periodika

20

Číslo periodika v rámci svazku

9

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

2515-2521

Kód UT WoS článku

000331729700018

EID výsledku v databázi Scopus

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