Transient Resonant Auger-Meitner Spectra of Photoexcited Thymine
Abstract
We present the first investigation of excited state dynamics by resonant Auger-Meitner spectroscopy (also known as resonant Auger spectroscopy) using the nucleobase thymine as an example. Thymine is photoexcited in the UV and probed with X-ray photon energies at and below the oxygen K-edge. After initial photoexcitation to a {\pi}{\pi}* excited state, thymine is known to undergo internal conversion to an n{\pi}* excited state with a strong resonance at the oxygen K-edge, red-shifted from the ground state {\pi}* resonances of thymine (see our previous study Wolf et al., Nat. Commun., 2017, 8, 29). We resolve and compare the Auger-Meitner electron spectra associated both with the excited state and ground state resonances, and distinguish participator and spectator decay contributions. Furthermore, we observe simultaneously with the decay of the n{\pi}* state signatures the appearance of additional resonant Auger-Meitner contributions at photon energies between the n{\pi}* state and the ground state resonances. We assign these contributions to population transfer from the n{\pi}* state to a {\pi}{\pi}* triplet state via intersystem crossing on the picosecond timescale based on simulations of the X-ray absorption spectra in the vibrationally hot triplet state. Moreover, we identify signatures from the initially excited {\pi}{\pi}* singlet state which we have not observed in our previous study.
Keywords
Cite
@article{arxiv.2009.14355,
title = {Transient Resonant Auger-Meitner Spectra of Photoexcited Thymine},
author = {Thomas J. A. Wolf and Alexander C. Paul and Sarai D. Folkestad and Rolf H. Myhre and James P. Cryan and Nora Berrah and Phil H. Bucksbaum and Sonia Coriani and Giacomo Coslovich and Raimund Feifel and Todd J. Martinez and Stefan P. Moeller and Melanie Mucke and Razib Obaid and Oksana Plekan and Richard J. Squibb and Henrik Koch and Markus Gühr},
journal= {arXiv preprint arXiv:2009.14355},
year = {2021}
}