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arXiv · 2505.07361

Valence photoelectron spectra of thiouracils in the gas phase

Dennis Mayer·Evgenii Titov·Fabiano Lever·Lisa Mehner·Marta L. Murillo-Sánchez·Constantin Walz·John Bozek·Peter Saalfrank·Markus Gühr
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Abstract

We present a combined experimental and theoretical study of the vibrationally resolved valence photoelectron spectra of the complete series of thiouracils (2-thiouracil, 4-thiouracil and 2,4-dithiouracil) for binding energies between 8 and 17 eV. The theoretical spectra were calculated using equation-of-motion coupled cluster theory for ionization potential (EOM-IP-CCSD) combined with the time-independent double-harmonic adiabatic Hessian approach. For all three thiouracils, the first ionization potential is found between 8.4 and 8.7 eV, which is 1 eV lower than for the canonical nucleobase uracil. Ionization bands up to 12 eV show strong vibrational progressions and are well reproduced by the calculations. These bands are attributed to the ionization of (primarily) sulfur- and oxygen-localized valence molecular orbitals. For higher binding energies, the calculations indicate that nonadiabatic couplings are important for the interpretation of the photoelectron spectra.

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Dennis Mayer, Evgenii Titov, Fabiano Lever, Lisa Mehner, Marta L. Murillo-Sánchez, Constantin Walz, John Bozek, Peter Saalfrank, Markus Gühr. 2025-05-12. Valence photoelectron spectra of thiouracils in the gas phase. https://doi.org/10.1063/5.0279536

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