| SZABLA, Rafal Kazimierz, Robert W. GÓRA, Jiří ŠPONER and Judit ŠPONEROVÁ. Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases. Chemistry - A European Journal. Weinheim: WILEY- VCH VERLAG GMBH, 2014, vol. 20, No 9, p. 2515-2521. ISSN 0947-6539. Available from: https://dx.doi.org/10.1002/chem.201304224. |
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@article{1184820,
author = {Szabla, Rafal Kazimierz and Góra, Robert W. and Šponer, Jiří and Šponerová, Judit},
article_location = {Weinheim},
article_number = {9},
doi = {http://dx.doi.org/10.1002/chem.201304224},
keywords = {isomerization; nucleobases; nucleotides; photochemistry; quantum chemistry},
language = {eng},
issn = {0947-6539},
journal = {Chemistry - A European Journal},
title = {Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases},
url = {http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf},
volume = {20},
year = {2014}
}
TY - JOUR
ID - 1184820
AU - Szabla, Rafal Kazimierz - Góra, Robert W. - Šponer, Jiří - Šponerová, Judit
PY - 2014
TI - Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases
JF - Chemistry - A European Journal
VL - 20
IS - 9
SP - 2515-2521
EP - 2515-2521
PB - WILEY- VCH VERLAG GMBH
SN - 09476539
KW - isomerization
KW - nucleobases
KW - nucleotides
KW - photochemistry
KW - quantum chemistry
UR - http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf
L2 - http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf
N2 - 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 be disregarded 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 with a 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 this photoreaction. Therefore, we conclude that the triplet reaction channel in DAMN might not be as prominent as was previously thought.
ER -
SZABLA, Rafal Kazimierz, Robert W. GÓRA, Jiří ŠPONER and Judit ŠPONEROVÁ. Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases. \textit{Chemistry - A European Journal}. Weinheim: WILEY- VCH VERLAG GMBH, 2014, vol.~20, No~9, p.~2515-2521. ISSN~0947-6539. Available from: https://dx.doi.org/10.1002/chem.201304224.
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