期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 107, 期 50, 页码 21453-21458出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1014982107
关键词
photodynamical simulation; photostability; ultrafast photodeactivation; nonadiabatic interactions; ab initio multireference methods
资金
- Austrian Science Fund [F16, F41, P18411-N19]
- Ministry of Education of the Czech Republic (Center for Biomolecules and Complex Molecular Systems) [LC512]
- Praemium Academiae of the Academy of Sciences of the Czech Republic
- Institute of Organic Chemistry and Biochemistry of the Academy of Sciences of the Czech Republic [Z40550506]
- Austrian Science Fund (FWF) [F16] Funding Source: Austrian Science Fund (FWF)
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.
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