Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (11): 2559-2564.doi: 10.3866/PKU.WHXB20111115

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Dynamics Simulation of Photophysical Deactivation Pathway for Stacked Thymines

DOU Yu-Sheng, LI Wei, YUAN Shuai, ZHANG Wen-Ying, LI An-Yang, SHU Kun-Xian, TANG Hong   

  1. Institute of High Performance Computing and Application, Research Center of Network and Computing, Chongqing University of Posts and Telecommunications, Chongqing 400065, P. R. China
  • Received:2011-05-24 Revised:2011-07-26 Published:2011-10-27
  • Contact: DOU Yu-Sheng E-mail:douys@cqupt.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21073242), Natural Science Foundation of Chongqing, China (cstc2011jjA00009) and Project of the Science Technology Foundation of Chongqing Education Committee, China (KJ100507).

Abstract: A semiclassical dynamics simulation study was undertaken to determine the photophysical deactivation of the lowest excited state of two stacked thymines. Only one thymine, referred to as T, was excited by a laser pulse and the other molecule, referred to as T′, remained in the ground state. The simulation results show that charge transfer between the two thymines because of a π-stacking interaction leads to the formation of an excimer state, which includes a negative T and a positive T′. Additionally, the simulation study indicates that a steric effect of the neighboring bases inhibits the out-of-plane deformation, which is essential in accessing the conical intersection between the lowest electronic-excited state and the ground state. The steric effect eventually leads to a longer electronic-excited state lifetime for the two stacked thymines. The simulation results reveal that when the interbase distance is less than 0.3 nm the molecule T has a remarkable deformation at its C5 and C6 sites resulting in charge recombination. The charge recombination ultimately makes the system electronically neutral. On the other hand, the molecule T′ has a strong twist about its C5′―C6′ bond in the proximity of the avoided crossing by which the system decays to the ground state. Finally, the two thymine molecules in their ground states recover their planar geometries.

Key words: Thymine, Semiclassical dynamic simulation, Charge transfer, Excimer, Deactivation

MSC2000: 

  • O641