| SZABLA, Rafal Kazimierz, Robert W. GORA a Jiří ŠPONER. Ultrafast excited-state dynamics of isocytosine. Physical Chemistry Chemical Physics. Cambridge: Royal Society of Chemistry, 2016, roč. 18, č. 30, s. 20208-20218. ISSN 1463-9076. Dostupné z: https://dx.doi.org/10.1039/c6cp01391k. |
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@article{1356118,
author = {Szabla, Rafal Kazimierz and Gora, Robert W. and Šponer, Jiří},
article_location = {Cambridge},
article_number = {30},
doi = {http://dx.doi.org/10.1039/c6cp01391k},
keywords = {PERTURBATION-THEORY; RELAXATION MECHANISMS; PREBIOTIC CHEMISTRY; MOLECULAR-DYNAMICS; COUPLED-CLUSTER; PROTON-TRANSFER; AB-INITIO; WATER; RNA; EFFICIENT},
language = {eng},
issn = {1463-9076},
journal = {Physical Chemistry Chemical Physics},
title = {Ultrafast excited-state dynamics of isocytosine},
url = {http://pubs.rsc.org/en/content/articlepdf/2016/cp/c6cp01391k},
volume = {18},
year = {2016}
}
TY - JOUR
ID - 1356118
AU - Szabla, Rafal Kazimierz - Gora, Robert W. - Šponer, Jiří
PY - 2016
TI - Ultrafast excited-state dynamics of isocytosine
JF - Physical Chemistry Chemical Physics
VL - 18
IS - 30
SP - 20208-20218
EP - 20208-20218
PB - Royal Society of Chemistry
SN - 14639076
KW - PERTURBATION-THEORY
KW - RELAXATION MECHANISMS
KW - PREBIOTIC CHEMISTRY
KW - MOLECULAR-DYNAMICS
KW - COUPLED-CLUSTER
KW - PROTON-TRANSFER
KW - AB-INITIO
KW - WATER
KW - RNA
KW - EFFICIENT
UR - http://pubs.rsc.org/en/content/articlepdf/2016/cp/c6cp01391k
L2 - http://pubs.rsc.org/en/content/articlepdf/2016/cp/c6cp01391k
N2 - The alternative nucleobase isocytosine has long been considered as a plausible component of hypothetical primordial informational polymers. To examine this hypothesis we investigated the excited-state dynamics of the two most abundant forms of isocytosine in the gas phase (keto and enol). Our surface-hopping nonadiabatic molecular dynamics simulations employing the algebraic diagrammatic construction to the second order [ADC(2)] method for the electronic structure calculations suggest that both tautomers undergo efficient radiationless deactivation to the electronic ground state with time constants which amount to tau(keto) = 182 fs and tau(enol) = 533 fs. The dominant photorelaxation pathways correspond to ring-puckering (pi pi* surface) and C = O stretching/N-H tilting (n pi* surface) for the enol and keto forms respectively. Based on these findings, we infer that isocytosine is a relatively photostable compound in the gas phase and in these terms resembles biologically relevant nucleobases. The estimated S-1 -> T-1 intersystem crossing rate constant of 8.02 x 10(10) s(-1) suggests that triplet states might also play an important role in the overall excited-state dynamics of the keto tautomer. The reliability of ADC(2)-based surface-hopping molecular dynamics simulations was tested against multireference quantum-chemical calculations and the potential limitations of the employed ADC(2) approach are briefly discussed.
ER -
SZABLA, Rafal Kazimierz, Robert W. GORA a Jiří ŠPONER. Ultrafast excited-state dynamics of isocytosine. \textit{Physical Chemistry Chemical Physics}. Cambridge: Royal Society of Chemistry, 2016, roč.~18, č.~30, s.~20208-20218. ISSN~1463-9076. Dostupné z: https://dx.doi.org/10.1039/c6cp01391k.
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