Photoinduced hydrogen dissociation in thymine predicted by coupled cluster theory

Eirik F. Kjønstad (), O. Jonathan Fajen, Alexander C. Paul, Sara Angelico, Dennis Mayer, Markus Gühr, Thomas J. A. Wolf, Todd J. Martínez () and Henrik Koch ()
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Eirik F. Kjønstad: Stanford University
O. Jonathan Fajen: Stanford University
Alexander C. Paul: Norwegian University of Science and Technology
Sara Angelico: Norwegian University of Science and Technology
Dennis Mayer: Deutsches Elektronen-Synchrotron DESY
Markus Gühr: Deutsches Elektronen-Synchrotron DESY
Thomas J. A. Wolf: Stanford University
Todd J. Martínez: Stanford University
Henrik Koch: Norwegian University of Science and Technology

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: Abstract The fate of thymine upon excitation by ultraviolet radiation has been the subject of intense debate. Today, it is widely believed that its ultrafast excited state gas phase decay stems from a radiationless transition from the bright ππ* state to a dark nπ* state. However, conflicting theoretical predictions have made the experimental data difficult to interpret. Here we simulate the early gas phase ultrafast dynamics in thymine at the highest level of theory to date. This is made possible by performing wavepacket dynamics with a recently developed coupled cluster method. Our simulation confirms an ultrafast ππ* to nπ* transition (τ = 41 ± 14 fs). Furthermore, the predicted oxygen-edge X-ray absorption spectra agree quantitatively with experiment. We also predict an as-yet uncharacterized πσ* channel that leads to hydrogen dissociation at one of the two N-H bonds. Similar behavior has been identified in other heteroaromatic compounds, including adenine, and several authors have speculated that a similar pathway may exist in thymine. However, this was never confirmed theoretically or experimentally. This prediction calls for renewed efforts to experimentally identify or exclude the presence of this channel.

Date: 2024
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DOI: 10.1038/s41467-024-54436-2

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