000626600 001__ 626600 000626600 005__ 20250907054602.0 000626600 0247_ $$2doi$$a10.1063/5.0279536 000626600 0247_ $$2datacite_doi$$a10.3204/PUBDB-2025-01501 000626600 0247_ $$2altmetric$$aaltmetric:177057579 000626600 0247_ $$2pmid$$apmid:40815564 000626600 037__ $$aPUBDB-2025-01501 000626600 041__ $$aEnglish 000626600 082__ $$a530 000626600 1001_ $$0P:(DE-H253)PIP1087484$$aMayer, Dennis$$b0$$eCorresponding author 000626600 245__ $$aValence photoelectron spectra of thiouracils in the gas phase 000626600 260__ $$aMelville, NY$$bAmerican Institute of Physics$$c2025 000626600 3367_ $$2DRIVER$$aarticle 000626600 3367_ $$2DataCite$$aOutput Types/Journal article 000626600 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article$$bjournal$$mjournal$$s1756900214_1757909 000626600 3367_ $$2BibTeX$$aARTICLE 000626600 3367_ $$2ORCID$$aJOURNAL_ARTICLE 000626600 3367_ $$00$$2EndNote$$aJournal Article 000626600 520__ $$aWe present a combined experimental and theoretical study of the vibrationally resolved valence photoelectron spectra of the complete series of thiouracils (2-thiouracil, 4-thiouracil, and 2,4-dithiouracil) for binding energies between 8 and 17 eV. The theoretical spectra were calculated using equation-of-motion coupled cluster theory for ionization potential combined with the time-independent double-harmonic adiabatic Hessian approach. For all three thiouracils, the first ionization potential is found between 8.4 and 8.7 eV, which is 1 eV lower than for the canonical nucleobase uracil. Ionization bands up to 12 eV show strong vibrational progressions and are well reproduced by the calculations. These bands are attributed to the ionization of (primarily) sulfur- and oxygen-localized valence molecular orbitals. For higher binding energies, the calculations indicate that nonadiabatic couplings are important for the interpretation of the photoelectron spectra. 000626600 536__ $$0G:(DE-HGF)POF4-631$$a631 - Matter – Dynamics, Mechanisms and Control (POF4-631)$$cPOF4-631$$fPOF IV$$x0 000626600 536__ $$0G:(GEPRIS)445713302$$aDFG project G:(GEPRIS)445713302 - Untersuchung der Dynamik von Thionukleobasen mittels Abfrage an der Schwefel L-Kante (445713302)$$c445713302$$x1 000626600 536__ $$0G:(GEPRIS)536025008$$aSFB 1636 B05 - Mechanismen photochemischer Reaktionen an metallischen Nanopartikeln (B05) (536025008)$$c536025008$$x2 000626600 536__ $$0G:(GEPRIS)535988987$$aSFB 1636 A03 - Bindungsaktivierung und molekulare Dynamik an Metallnanopartikeln untersucht mittels Röntgenspektroskopie (A03) (535988987)$$c535988987$$x3 000626600 693__ $$0EXP:(DE-MLZ)External-20140101$$5EXP:(DE-MLZ)External-20140101$$eMeasurement at external facility$$x0 000626600 7001_ $$0P:(DE-H253)PIP1112360$$aTitov, Evgenii$$b1$$eCorresponding author 000626600 7001_ $$0P:(DE-H253)PIP1087654$$aLever, Fabiano$$b2 000626600 7001_ $$0P:(DE-H253)PIP1089452$$aMurillo Sánchez, Marta$$b3 000626600 7001_ $$0P:(DE-HGF)0$$aMehner, Lisa$$b4 000626600 7001_ $$0P:(DE-HGF)0$$aWalz, Constantin$$b5 000626600 7001_ $$0P:(DE-H253)PIP1009440$$aBozek, John$$b6 000626600 7001_ $$0P:(DE-HGF)0$$aSaalfrank, Peter$$b7 000626600 7001_ $$0P:(DE-H253)PIP1084094$$aGuehr, Markus$$b8 000626600 773__ $$0PERI:(DE-600)1473050-9$$a10.1063/5.0279536$$p074301$$tThe journal of chemical physics$$v163$$x0021-9606$$y2025 000626600 8564_ $$uhttps://bib-pubdb1.desy.de/record/626600/files/HTML-Approval_of_scientific_publication.html 000626600 8564_ $$uhttps://bib-pubdb1.desy.de/record/626600/files/PDF-Approval_of_scientific_publication.pdf 000626600 8564_ $$uhttps://bib-pubdb1.desy.de/record/626600/files/Mayer_2025.pdf$$yOpenAccess 000626600 8564_ $$uhttps://bib-pubdb1.desy.de/record/626600/files/Mayer_2025.pdf?subformat=pdfa$$xpdfa$$yOpenAccess 000626600 909CO $$ooai:bib-pubdb1.desy.de:626600$$pdnbdelivery$$pdriver$$pVDB$$popen_access$$popenaire 000626600 9101_ $$0I:(DE-588b)2008985-5$$6P:(DE-H253)PIP1087484$$aDeutsches Elektronen-Synchrotron$$b0$$kDESY 000626600 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1087484$$aExternal Institute$$b0$$kExtern 000626600 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1112360$$aExternal Institute$$b1$$kExtern 000626600 9101_ $$0I:(DE-588b)2008985-5$$6P:(DE-H253)PIP1087654$$aDeutsches Elektronen-Synchrotron$$b2$$kDESY 000626600 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1087654$$aExternal Institute$$b2$$kExtern 000626600 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1089452$$aExternal Institute$$b3$$kExtern 000626600 9101_ $$0I:(DE-588)1043621512$$6P:(DE-H253)PIP1089452$$aEuropean XFEL$$b3$$kXFEL.EU 000626600 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1009440$$aExternal Institute$$b6$$kExtern 000626600 9101_ $$0I:(DE-588b)2008985-5$$6P:(DE-H253)PIP1084094$$aDeutsches Elektronen-Synchrotron$$b8$$kDESY 000626600 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1084094$$aExternal Institute$$b8$$kExtern 000626600 9101_ $$0I:(DE-588)1043621512$$6P:(DE-H253)PIP1084094$$aEuropean XFEL$$b8$$kXFEL.EU 000626600 9131_ $$0G:(DE-HGF)POF4-631$$1G:(DE-HGF)POF4-630$$2G:(DE-HGF)POF4-600$$3G:(DE-HGF)POF4$$4G:(DE-HGF)POF$$aDE-HGF$$bForschungsbereich Materie$$lVon Materie zu Materialien und Leben$$vMatter – Dynamics, Mechanisms and Control$$x0 000626600 9141_ $$y2025 000626600 915__ $$0StatID:(DE-HGF)0200$$2StatID$$aDBCoverage$$bSCOPUS$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)0160$$2StatID$$aDBCoverage$$bEssential Science Indicators$$d2025-01-06 000626600 915__ $$0LIC:(DE-HGF)CCBY4$$2HGFVOC$$aCreative Commons Attribution CC BY 4.0 000626600 915__ $$0StatID:(DE-HGF)0600$$2StatID$$aDBCoverage$$bEbsco Academic Search$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)0100$$2StatID$$aJCR$$bJ CHEM PHYS : 2022$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)0113$$2StatID$$aWoS$$bScience Citation Index Expanded$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)0150$$2StatID$$aDBCoverage$$bWeb of Science Core Collection$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)9900$$2StatID$$aIF < 5$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)0510$$2StatID$$aOpenAccess 000626600 915__ $$0StatID:(DE-HGF)0030$$2StatID$$aPeer Review$$bASC$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)1150$$2StatID$$aDBCoverage$$bCurrent Contents - Physical, Chemical and Earth Sciences$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)0430$$2StatID$$aNational-Konsortium$$d2025-01-06$$wger 000626600 915__ $$0StatID:(DE-HGF)0300$$2StatID$$aDBCoverage$$bMedline$$d2025-01-06 000626600 915__ $$0StatID:(DE-HGF)0199$$2StatID$$aDBCoverage$$bClarivate Analytics Master Journal List$$d2025-01-06 000626600 9201_ $$0I:(DE-H253)FS-FLASH-20140814$$kFS-FLASH$$lFS-FLASH$$x0 000626600 980__ $$ajournal 000626600 980__ $$aVDB 000626600 980__ $$aUNRESTRICTED 000626600 980__ $$aI:(DE-H253)FS-FLASH-20140814 000626600 9801_ $$aFullTexts