{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,7,30]],"date-time":"2025-07-30T11:23:54Z","timestamp":1753874634384,"version":"3.41.2"},"reference-count":56,"publisher":"AIP Publishing","issue":"7","funder":[{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-AC02-06CH11357"],"award-info":[{"award-number":["DE-AC02-06CH11357"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000271","name":"Science and Technology Facilities Council","doi-asserted-by":"publisher","award":["N\/A"],"award-info":[{"award-number":["N\/A"]}],"id":[{"id":"10.13039\/501100000271","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2024,2,21]]},"abstract":"<jats:p>Resonant Auger processes provide a unique perspective on electronic interactions and excited vibrational and electronic states of molecular ions. Here, new data are presented on the resonant Auger decay of excited CH3I in the region just below the I 4d\u22121 ionization threshold. The resonances include the Rydberg series converging to the five spin\u2013orbit and ligand-field split CH3I (I 4d\u22121) thresholds, as well as resonances corresponding to excitation from the I 4d5\/2,3\/2 orbitals into the \u03c3* lowest unoccupied molecular orbital. This study focuses on participator decay that populates the lowest lying states of CH3I+, in particular, the X\u03032E3\/2 and 2E1\/2 states, and on spectator decay that populates the lowest-lying (CH3I2+)\u03c3* states of CH3I+. The CH3I (I 4d\u22121)\u03c3* resonances are broad, and dissociation to CH3 + I competes with the autoionization of the core-excited states. Auger decay as the molecule dissociates produces a photoelectron spectrum with a long progression (up to v3+ \u223c 25) in the C\u2013I stretching mode of the X\u03032E3\/2 and 2E1\/2 states, providing insights into the shape of the dissociative core-excited surface. The observed spectator decay processes indicate that CH3I+ is formed on the repulsive wall of the lower-lying (CH3I2+)\u03c3* potentials, and the photon-energy dependence of the processes provides insights into the relative slopes of the (4d\u22121)\u03c3* and (CH3I2+)\u03c3* potential surfaces. Data are also presented for the spectator decay of higher lying CH3I (I 4d\u22121)nl Rydberg resonances. Photoelectron angular distributions for the resonant Auger processes provide additional information that helps distinguish these processes from the direct ionization signal.<\/jats:p>","DOI":"10.1063\/5.0190794","type":"journal-article","created":{"date-parts":[[2024,2,20]],"date-time":"2024-02-20T11:29:31Z","timestamp":1708428571000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":3,"title":["Resonant Auger decay of dissociating CH3I near the I 4d threshold"],"prefix":"10.1063","volume":"160","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8282-1026","authenticated-orcid":false,"given":"Stephen T.","family":"Pratt","sequence":"first","affiliation":[{"name":"Chemical Sciences and Engineering Division, Argonne National Laboratory 1 , Lemont, Illinois 60439, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2152-261X","authenticated-orcid":false,"given":"Ugo","family":"Jacovella","sequence":"additional","affiliation":[{"name":"Institut des Sciences Mol\u00e9culaires d\u2019Orsay, CNRS, Universit\u00e9 Paris-Saclay 2 , F-91405 Orsay, France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9658-2436","authenticated-orcid":false,"given":"B\u00e9renger","family":"Gans","sequence":"additional","affiliation":[{"name":"Institut des Sciences Mol\u00e9culaires d\u2019Orsay, CNRS, Universit\u00e9 Paris-Saclay 2 , F-91405 Orsay, France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7486-7238","authenticated-orcid":false,"given":"John D.","family":"Bozek","sequence":"additional","affiliation":[{"name":"Synchrotron SOLEIL, L\u2019Orme des Merisiers 3 , D\u00e9partmentale 128, 91190 Saint-Aubin, France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1351-605X","authenticated-orcid":false,"given":"David M. 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