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The experiments are supported by extensive coupled cluster calculations on ThSO, ThSO\u2212, ThS2, and ThS2\u2212, as well as the oxygen congeners ThO2 and ThO2\u2212. The ab\u00a0initio calculations, which included complete basis set extrapolations, spin\u2013orbit effects using four-component coupled cluster, and higher-order correlation contributions through CCSDT(Q), yielded an adiabatic electron affinity for ThO2 that was within 0.02\u00a0eV of the previously determined experimental value. The singly occupied molecular orbital (SOMO) in all three anions corresponds primarily to the 7s orbital on Th. Successive substitution of S for each O in ThO2 leads to larger electron affinities and smaller bond angles in the neutral molecules, but larger angles in the anions. As demonstrated by Franck\u2013Condon simulations of the spectra using the CCSD(T) spectroscopic constants, substitution of O by S significantly complicates the resulting detachment spectra due to the lower vibrational frequencies in the sulfur species. Overall the calculated vertical detachment energies are in very good agreement with the experiment. In addition to the adiabatic electron affinities of each species, atomization energies and heats of formation have also been determined via the FPD approach with expected uncertainties of 1\u20132 kcal\/mol.<\/jats:p>","DOI":"10.1063\/5.0229157","type":"journal-article","created":{"date-parts":[[2024,10,10]],"date-time":"2024-10-10T12:20:16Z","timestamp":1728562816000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":4,"title":["Anion photoelectron spectroscopy and chemical bonding of ThS2\u2212 and ThSO\u2212"],"prefix":"10.1063","volume":"161","author":[{"given":"Mary","family":"Marshall","sequence":"first","affiliation":[{"name":"Department of Chemistry, Johns Hopkins University 1 , Baltimore, Maryland 21218,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4395-9102","authenticated-orcid":false,"given":"Zhaoguo","family":"Zhu","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Johns Hopkins University 1 , Baltimore, Maryland 21218,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0004-1373-5169","authenticated-orcid":false,"given":"Truong-Son","family":"Nguyen","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Washington State University 2 , Pullman, Washington 99162,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Burak A.","family":"Tufekci","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Johns Hopkins University 1 , Baltimore, Maryland 21218,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7388-8165","authenticated-orcid":false,"given":"Kathryn","family":"Foreman","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Johns Hopkins University 1 , Baltimore, Maryland 21218,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4901-3235","authenticated-orcid":false,"given":"Kirk A.","family":"Peterson","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Washington State University 2 , Pullman, Washington 99162,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2858-6352","authenticated-orcid":false,"given":"Kit H.","family":"Bowen","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Johns Hopkins University 1 , Baltimore, Maryland 21218,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2024,10,10]]},"reference":[{"key":"2024101010151649900_c1","volume-title":"The Chemistry of the Actinide and Transactinide Elements","year":"2006","edition":"3"},{"key":"2024101010151649900_c2","doi-asserted-by":"publisher","first-page":"669","DOI":"10.1016\/j.jallcom.2007.04.100","volume":"451","year":"2008","journal-title":"J.\u00a0Alloys Compd."},{"key":"2024101010151649900_c3","doi-asserted-by":"publisher","first-page":"324","DOI":"10.1016\/j.jnucmat.2011.04.060","volume":"414","year":"2011","journal-title":"J.\u00a0Nucl. 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