| SZABLA, Rafal Kazimierz, Judit ŠPONEROVÁ, Jiří ŠPONER, Andrzej SOBOLEWSKI and Robert W. GÓRA. Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines. Physical Chemistry Chemical Physics. Cambridge: Royal Society of Chemistry, 2014, vol. 16, No 33, p. 17617-17626. ISSN 1463-9076. Available from: https://dx.doi.org/10.1039/c4cp02074j. |
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@article{1200023,
author = {Szabla, Rafal Kazimierz and Šponerová, Judit and Šponer, Jiří and Sobolewski, Andrzej and Góra, Robert W.},
article_location = {Cambridge},
article_number = {33},
doi = {http://dx.doi.org/10.1039/c4cp02074j},
keywords = {PROTON-TRANSFER PROCESSES; INDOLE-WATER CLUSTERS; CHEMICAL EVOLUTION; PROGRAM SYSTEM; GAS-PHASE; ULTRAFAST DYNAMICS; BUILDING-BLOCKS; EXCITED-STATES; EARLY EARTH; PYRROLE},
language = {eng},
issn = {1463-9076},
journal = {Physical Chemistry Chemical Physics},
title = {Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines},
url = {http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP02074J#!divAbstract},
volume = {16},
year = {2014}
}
TY - JOUR
ID - 1200023
AU - Szabla, Rafal Kazimierz - Šponerová, Judit - Šponer, Jiří - Sobolewski, Andrzej - Góra, Robert W.
PY - 2014
TI - Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines
JF - Physical Chemistry Chemical Physics
VL - 16
IS - 33
SP - 17617-17626
EP - 17617-17626
PB - Royal Society of Chemistry
SN - 14639076
KW - PROTON-TRANSFER PROCESSES
KW - INDOLE-WATER CLUSTERS
KW - CHEMICAL EVOLUTION
KW - PROGRAM SYSTEM
KW - GAS-PHASE
KW - ULTRAFAST DYNAMICS
KW - BUILDING-BLOCKS
KW - EXCITED-STATES
KW - EARLY EARTH
KW - PYRROLE
UR - http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP02074J#!divAbstract
L2 - http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP02074J#!divAbstract
N2 - 4-Aminoimidazole-5-carbonitrile (AICN) was suggested as a prebiotically plausible precursor of purine nucleobases and nucleotides. Although it can be formed in a sequence of photoreactions, AICN is immune to further irradiation with UV-light. We present state-of-the-art multi-reference quantum-chemical calculations of potential energy surface cuts and conical intersection optimizations to explain the molecular mechanisms underlying the photostability of this compound. We have identified the N-H bond stretching and ring-puckering mechanisms that should be responsible for the photochemistry of AICN in the gas phase. We have further considered the photochemistry of AICN-water clusters, while including up to six explicit water molecules. The calculations reveal charge transfer to solvent followed by formation of an H3O+ cation, both of which occur on the (1)pi sigma* hypersurface. Interestingly, a second proton transfer to an adjacent water molecule leads to a (1)pi sigma*/S-o conical intersection. We suggest that this electron-driven proton relay might be characteristic of low-lying lice states in chromophore water clusters. Owing to its nature, this mechanism might also be responsible for the photostability of analogous organic molecules in bulk water.
ER -
SZABLA, Rafal Kazimierz, Judit ŠPONEROVÁ, Jiří ŠPONER, Andrzej SOBOLEWSKI and Robert W. GÓRA. Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines. \textit{Physical Chemistry Chemical Physics}. Cambridge: Royal Society of Chemistry, 2014, vol.~16, No~33, p.~17617-17626. ISSN~1463-9076. Available from: https://dx.doi.org/10.1039/c4cp02074j.
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