Titel
Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases
... show all
Abstract
A comprehensive effort in photodynamical ab initio simulations of the ultrafast deactivation pathways for all five nucleobases adenine, guanine, cytosine, thymine, and uracil is reported. These simulations are based on a complete nonadiabatic surface-hopping approach using extended multiconfigurational wave functions. Even though all five nucleobases share the basic internal conversion mechanisms, the calculations show a distinct grouping into purine and pyrimidine bases as concerns the complexity of the photodynamics. The purine bases adenine and guanine represent the most simple photodeactivation mechanism with the dynamics leading along a diabatic pi pi* path directly and without barrier to the conical intersection seam with the ground state. In the case of the pyrimidine bases, the dynamics starts off in much flatter regions of the pi pi* energy surface due to coupling of several states. This fact prohibits a clear formation of a single reaction path. Thus, the photodynamics of the pyrimidine bases is much richer and includes also n pi* states with varying importance, depending on the actual nucleobase considered. Trapping in local minima may occur and, therefore, the deactivation time to the ground state is also much longer in these cases. Implications of these findings are discussed (i) for identifying structural possibilities where singlet/triplet transitions can occur because of sufficient retention time during the singlet dynamics and (ii) concerning the flexibility of finding other deactivation pathways in substituted pyrimidines serving as candidates for alternative nucleobases.
Stichwort
photodynamical simulationphotostabilityultrafast photodeactivationnonadiabatic interactionsab initio multireference methods
Objekt-Typ
Sprache
Englisch [eng]
Persistent identifier
https://phaidra.univie.ac.at/o:243890
Erschienen in
Titel
Proceedings of the National Academy of Sciences of the United States of America (PNAS)
Band
107
Ausgabe
50
Seitenanfang
21453
Seitenende
21458
Erscheinungsdatum
01.03.2010
Universität Wien | Universitätsring 1 | 1010 Wien | T +43-1-4277-0