{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,31]],"date-time":"2025-12-31T04:22:09Z","timestamp":1767154929035,"version":"build-2238731810"},"reference-count":55,"publisher":"AIP Publishing","issue":"17","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2008,11,7]]},"abstract":"<jats:p>Electronic structures of trans- and cis-dichloroethylenes and tetrachloroethylene were studied using symmetry-adapted cluster configuration interaction theory. Basis sets up to the aug-cc-pVTZ of Dunning, Jr., augmented with appropriate Rydberg functions were used for the calculations. The results derived in the present study show good agreement with the available experimental values. In all cases, the main bright excitation was the \u03c0\u2192\u03c0\u2217 transition. The other vertical excitations, \u03c0\u2192\u03c3\u2217, n\u2192\u03c3\u2217, and n\u2192\u03c0\u2217, which have not been studied before, were also investigated. First Rydberg series involving transitions from the \u03c0 orbitals to one 3s, three 3p, and five 3d orbitals were identified clearly. Several new assignments and reassignments of features in the experimental spectra were suggested. Contrary to earlier prediction, two n-\u03c3\u2217 states, along with a \u03c0-\u03c3\u2217 state in the dichloroethylenes, were calculated to be located above the main \u03c0-\u03c0\u2217 state. Accordingly, crossing between both the n-\u03c3\u2217 states with the bright \u03c0-\u03c0\u2217 state is highly likely, unlike conclusions made in the earlier studies. This indicates that the photodissociation mechanism proposed by the earlier calculations warrants revision. Several low-lying triplet excited states were also studied. Electronic spectra of trans-1-chloro-2-fluoroethylene and cis-1-chloro-2-fluoroethylene were also calculated. The \u03c0\u2192\u03c0\u2217 transitions of these haloethylenes are compared and interpreted in terms of the inductive and resonance effects.<\/jats:p>","DOI":"10.1063\/1.3002911","type":"journal-article","created":{"date-parts":[[2008,11,5]],"date-time":"2008-11-05T20:19:06Z","timestamp":1225916346000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":15,"title":["Electronic transitions in\n                    <i>cis<\/i>\n                    - and\n                    <i>trans<\/i>\n                    -dichloroethylenes and tetrachloroethylene"],"prefix":"10.1063","volume":"129","author":[{"given":"Sundaram","family":"Arulmozhiraja","sequence":"first","affiliation":[{"name":"Kyoto University 1 Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, , Katsura, Nishikyou-ku, Kyoto 615-8510, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Masahiro","family":"Ehara","sequence":"additional","affiliation":[{"name":"Institute for Molecular Science 2 , Nishigo-Naka 38, Myodaiji, Okazaki 444-8585, Japan"},{"name":"CREST 3 JST, , Sanbancho-5, Chiyoda-ku, Tokyo 102-0075, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hiroshi","family":"Nakatsuji","sequence":"additional","affiliation":[{"name":"CREST 3 JST, , Sanbancho-5, Chiyoda-ku, Tokyo 102-0075, Japan"},{"name":"Quantum Chemistry Research Institute 4 , Kyodai Katsura Venture Plaza 106, Goryo Oohara 1-36, Nishikyo-ku 615-8245, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2008,11,5]]},"reference":[{"key":"2023062604061538900_c1","doi-asserted-by":"publisher","first-page":"536","DOI":"10.1063\/1.1749721","volume":"3","year":"1935","journal-title":"J. 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