{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,10]],"date-time":"2025-12-10T08:38:25Z","timestamp":1765355905846,"version":"3.41.2"},"reference-count":54,"publisher":"AIP Publishing","issue":"13","funder":[{"name":"ASTRID2 Synchrotron Facility Grant of beamtime"},{"name":"Elettra Synchrotron Facility Grant of beamtime"},{"DOI":"10.13039\/501100000780","name":"European Union","doi-asserted-by":"crossref","award":["grant agreement n\u00c2\u00ba 312284"],"award-info":[{"award-number":["grant agreement n\u00c2\u00ba 312284"]}],"id":[{"id":"10.13039\/501100000780","id-type":"DOI","asserted-by":"crossref"}]},{"name":"MIUR Italy","award":["project PON01-01078\/8"],"award-info":[{"award-number":["project PON01-01078\/8"]}]},{"name":"Portuguese Foundation for Science and technology, FCT-MEC","award":["grants PEst-OE\/FIS\/UI0068\/2014; PTDC\/FIS-ATO\/1832\/2012"],"award-info":[{"award-number":["grants PEst-OE\/FIS\/UI0068\/2014; PTDC\/FIS-ATO\/1832\/2012"]}]},{"name":"UK NSCCS Super-computing Facility allocation of CPU time"}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2015,4,7]]},"abstract":"<jats:p>Identification of many Rydberg states in iodobenzene, especially from the first and fourth ionization energies (IE1 and IE4, X2B1 and C2B1), has become possible using a new ultraviolet (UV) and vacuum-ultraviolet (VUV) absorption spectrum, in the region 29 000-87 000 cm\u22121 (3.60-10.79 eV), measured at room temperature with synchrotron radiation. A few Rydberg states based on IE2 (A2A2) were found, but those based on IE3 (B2B2) are undetectable. The almost complete absence of observable Rydberg states relating to IE2 and IE3 (A2A2 and B2B2, respectively) is attributed to them being coupled to the near-continuum, high-energy region of Rydberg series converging on IE1. Theoretical studies of the UV and VUV spectra used both time-dependent density functional (TDDFT) and multi-reference multi-root doubles and singles-configuration interaction methods. The theoretical adiabatic excitation energies, and their corresponding vibrational profiles, gave a satisfactory interpretation of the experimental results. The calculations indicate that the UV onset contains both 11B1 and 11B2 states with very low oscillator strength, while the 21B1 state was found to lie under the lowest \u03c0\u03c0\u2217 11A1 state. All three of these 1B1 and 1B2 states are excitations into low-lying \u03c3\u2217 orbitals. The strongest VUV band near 7 eV contains two very strong \u03c0\u03c0\u2217 valence states, together with other weak contributors. The lowest Rydberg 4b16s state (31B1) is very evident as a sharp multiplet near 6 eV; its position and vibrational structure are well reproduced by the TDDFT results.<\/jats:p>","DOI":"10.1063\/1.4916121","type":"journal-article","created":{"date-parts":[[2015,4,1]],"date-time":"2015-04-01T17:02:49Z","timestamp":1427907769000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":68,"title":["Interpretation of the vacuum ultraviolet photoabsorption spectrum of iodobenzene by <i>ab initio<\/i> computations"],"prefix":"10.1063","volume":"142","author":[{"given":"Michael H.","family":"Palmer","sequence":"first","affiliation":[{"name":"University of Edinburgh 1 School of Chemistry, , Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland, United Kingdom"}]},{"given":"Trevor","family":"Ridley","sequence":"additional","affiliation":[{"name":"University of Edinburgh 1 School of Chemistry, , Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland, United Kingdom"}]},{"given":"S\u00f8ren Vr\u00f8nning","family":"Hoffmann","sequence":"additional","affiliation":[{"name":"Aarhus University 2 Department of Physics and Astronomy, ISA, , Ny Munkegade 120, DK-8000 Aarhus C, Denmark"}]},{"given":"Nykola C.","family":"Jones","sequence":"additional","affiliation":[{"name":"Aarhus University 2 Department of Physics and Astronomy, ISA, , Ny Munkegade 120, DK-8000 Aarhus C, Denmark"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4376-808X","authenticated-orcid":false,"given":"Marcello","family":"Coreno","sequence":"additional","affiliation":[{"name":"CNR-ISM 3 , Montelibretti, c\/o Laboratorio Elettra, Trieste, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9491-0173","authenticated-orcid":false,"given":"Monica","family":"de Simone","sequence":"additional","affiliation":[{"name":"CNR-IOM 4 Laboratorio TASC, Trieste, Italy"}]},{"given":"Cesare","family":"Grazioli","sequence":"additional","affiliation":[{"name":"CNR-IOM 4 Laboratorio TASC, Trieste, Italy"},{"name":"University of Trieste 5 Department of Chemical and Pharmaceutical Sciences, , Trieste, Italy"}]},{"given":"Malgorzata","family":"Biczysko","sequence":"additional","affiliation":[{"name":"6National Research Council ICCOM-CNR, UOS di Pisa, Via G. 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