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Volume 228, 2021

Effect of dynamic correlation on the ultrafast relaxation of uracil in the gas phase

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Abstract

The photophysics and photochemistry of DNA/RNA nucleobases have been extensively investigated during the past two decades, both experimentally and theoretically. The ultrafast relaxation of the canonical nucleobases following photoexcitation is of significant interest when it comes to understanding how nature has ensured their photostability. Here we study the excited state dynamics of uracil which is a nucleobase found in RNA. Although theory and experiment have shed significant light on understanding the photoexcited dynamics of uracil, there are still disagreements in the literature about specific details. In order to examine how the dynamics is influenced by the underlying electronic structure theory, we have performed non-adiabatic excited state dynamics simulations of uracil using on-the-fly trajectory surface hopping methodology on potential energy surfaces calculated at different electronic structure theory levels (CASSCF, MRCIS, XMS-CASPT2, TD-DFT). These simulations reveal that the dynamics are very sensitive to the underlying electronic structure theory, with the multi-reference theory levels that include dynamic correlation, predicting that there is no trapping on the absorbing S2 state, in contrast to predictions from lower level electronic structure results. The dynamics are instead governed by ultrafast decay to the ground state, or trapping on the dark S1 state.

Graphical abstract: Effect of dynamic correlation on the ultrafast relaxation of uracil in the gas phase

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Article information


Submitted
22 Sep 2020
Accepted
27 Oct 2020
First published
30 Oct 2020

Faraday Discuss., 2021,228, 266-285
Article type
Paper

Effect of dynamic correlation on the ultrafast relaxation of uracil in the gas phase

P. Chakraborty, Y. Liu, T. Weinacht and S. Matsika, Faraday Discuss., 2021, 228, 266 DOI: 10.1039/D0FD00110D

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