A theoretical study on the excited-state deactivation paths for the A–5FU dimer

Literature Information

Publication Date 2021-06-28
DOI 10.1039/D1CP00030F
Impact Factor 3.676
Authors

Xue-fang Yu, Ting-he Fu, Bo Xiao, Hong-yuan Yu, Qingzhong Li


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Abstract

The photostability of DNA plays a key role in the normal function of organisms. A–5FU is a base pair derivative of the A–T dimer where the methyl group is replaced by a F atom. Here, accurate static TDDFT calculations and non-adiabatic dynamic simulations are used to systematically investigate the excited-state decay paths of the A–5FU dimer related to the proton transfer and the out-of-plane twisting deformation motion of A and 5FU in the 1ππ* and 1nπ* states. CC2 is used to check the accuracy of the current TDDFT calculations. Our results show that the deformation of the CC or CN double bond in A and 5FU provides an efficient pathway for the depopulation of the lowest excited states, which can compete with the excited-state proton transfer paths in the dimer. This finding indicates that monomer-like decay paths could be important for the photostability of weakly hydrogen-bonded DNA base pairs and provide a new insight into the excited-state decay paths in base pairs and their analogues.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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