Volume 228, 2021

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

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

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
22 ספט 2020
Accepted
27 אוק 2020
First published
30 אוק 2020

Faraday Discuss., 2021,228, 266-285

Author version available

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements