New Insights into the State Trapping of UV-Excited Thymine

Ljiljana Stojanović (1) , Shuming Bai (1) , Jayashree Nagesh , Artur F. Izmaylov , Rachel Crespo-Otero (2) , Hans Lischka (3) , Mario Barbatti (1)

1 ICR - Institut de Chimie Radicalaire
2 Max-Planck-Institut für Kohlenforschung (Coal Research)
3 Institute for theoretical Chemistry

After UV excitation, gas phase thymine returns to a ground state in 5 to 7 ps, showing multiple time constants. There is no consensus on the assignment of these processes, with a dispute between models claiming that thymine is trapped either in the first (S1) or in the second (S2) excited states. In the present study, a nonadiabatic dynamics simulation of thymine is performed on the basis of ADC(2) surfaces, to understand the role of dynamic electron correlation on the deactivation pathways. The results show that trapping in S2 is strongly reduced in comparison to previous simulations considering only non-dynamic electron correlation on CASSCF surfaces. The reason for the difference is traced back to the energetic cost for formation of a CO π bond in S2.

Mots clés: computational theoretical chemistry; nonadiabatic dynamics; nucleobases; photochemistry; surface hopping; thymine; ultrafast processes

Domaines: Chimie théorique et/ou physique

Ljiljana Stojanović, Shuming Bai, Jayashree Nagesh, Artur F. Izmaylov, Rachel Crespo-Otero, et al.. New Insights into the State Trapping of UV-Excited Thymine. Molecules, 2016, 21 (11), pp.1603. ⟨hal-01415840⟩