{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,18]],"date-time":"2025-10-18T14:54:44Z","timestamp":1760799284077,"version":"3.41.2"},"reference-count":80,"publisher":"AIP Publishing","issue":"16","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2007,10,28]]},"abstract":"<jats:p>Extended complete active space self-consistent field (CASSCF), multireference configuration interaction with singles and doubles (MR-CISD), and multireference average quadratic coupled cluster (MR-AQCC) calculations have been performed on the ground (S0) and first excited (n\u03c3*,S1) states of the CF3Cl molecule. Full geometry optimizations have been carried out for S0 as well as \u201crelaxed\u201d potential energy calculations for both states, along the C\u2013Cl bond distance. Vertical excitation energies (\u0394Evertical), dissociation energies (\u0394Ediss), dissociation enthalpies (\u0394Hdiss), and the oscillator strength (f) have also been computed. Basis set effects, basis set superposition error (BSSE), and spin-orbit and size-extensivity corrections have also been considered. The general agreement between theoretical and available experimental results is very good. The best results for the equilibrium geometrical parameters of S0 (at MR-AQCC\u2215aug-cc-pVTZ+d level) are 1.762 and 1.323\u00c5, for the C\u2013Cl and C\u2013F bond distances, respectively, while the corresponding experimental values are 1.751 and 1.328\u00c5. The \u2220ClCF and \u2220FCF bond angles are in excellent agreement with the corresponding experimental values (110.3\u00b0 and 108.6\u00b0). The best calculated values for \u0394Evertical, \u0394Hdiss, and f are 7.63eV [at the MR-AQCC\u2215aug-cc-pV(T+d)Z level], 3.59eV[MR-AQCC\u2215aug-cc-pV(T+d)Z\u2008level+spin-orbit and BSSE corrections], and 2.74\u00d710\u22123 (MR-CISD\/cc-pVTZ), in comparison with the corresponding experimental values of 7.7\u00b10.1eV, 3.68eV, and 3.12\u00d710\u22123\u00b12.50\u00d710\u22124. The results concerning the potential energy curves for S0 and S1 show a tendency toward the nonoccurrence of crossing between these two states (in the intermediate region along the C\u2013Cl coordinate), as the basis set size increases. Such tendency is accompanied by a decreasing well depth for the S1 state. Dynamic electronic correlation (especially at the MR-AQCC level) is also an important factor toward an absence of crossing along the C\u2013Cl coordinate. Further investigations of a possible crossing using gradient driven techniques (at CASSCF and MR-CISD levels) seem to confirm its absence.<\/jats:p>","DOI":"10.1063\/1.2800020","type":"journal-article","created":{"date-parts":[[2007,10,30]],"date-time":"2007-10-30T23:35:55Z","timestamp":1193787355000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":18,"title":["Dissociation of ground and n\u03c3* states of CF3Cl using multireference configuration interaction with singles and doubles and with multireference average quadratic coupled cluster extensivity corrections"],"prefix":"10.1063","volume":"127","author":[{"suffix":"Jr.","given":"Juracy R.","family":"Lucena","sequence":"first","affiliation":[{"name":"Universidade Federal da Para\u00edba Departamento de Qu\u00edmica, CCEN, , Jo\u00e3o Pessoa, Para\u00edba 58036-300 Brazil"}]},{"given":"Elizete","family":"Ventura","sequence":"additional","affiliation":[{"name":"Universidade Federal da Para\u00edba Departamento de Qu\u00edmica, CCEN, , Jo\u00e3o Pessoa, Para\u00edba 58036-300 Brazil"}]},{"given":"Silmar A.","family":"do Monte","sequence":"additional","affiliation":[{"name":"Universidade Federal da Para\u00edba Departamento de Qu\u00edmica, CCEN, , Jo\u00e3o Pessoa, Para\u00edba 58036-300 Brazil"}]},{"given":"Regiane C. M. U.","family":"Ara\u00fajo","sequence":"additional","affiliation":[{"name":"Universidade Federal da Para\u00edba Departamento de Qu\u00edmica, CCEN, , Jo\u00e3o Pessoa, Para\u00edba 58036-300 Brazil"}]},{"given":"Mozart N.","family":"Ramos","sequence":"additional","affiliation":[{"name":"Universidade Federal de Pernambuco Departamento de Qu\u00edmica Fundamental, , Recife, Pernambuco 50739-901, Brazil"}]},{"given":"Rui","family":"Fausto","sequence":"additional","affiliation":[{"name":"University of Coimbra Department of Chemistry (CQC), , 3004-535 Coimbra, Portugal"}]}],"member":"317","published-online":{"date-parts":[[2007,10,30]]},"reference":[{"key":"2023080208561230100_c1","doi-asserted-by":"publisher","first-page":"810","DOI":"10.1038\/249810a0","volume":"249","year":"1974","journal-title":"Nature (London)"},{"key":"2023080208561230100_c2","doi-asserted-by":"publisher","first-page":"731","DOI":"10.1146\/annurev.physchem.42.1.731","volume":"42","year":"1991","journal-title":"Annu. Rev. Phys. Chem."},{"key":"2023080208561230100_c3","doi-asserted-by":"publisher","first-page":"433","DOI":"10.1021\/j100286a035","volume":"91","year":"1987","journal-title":"J. Phys. Chem."},{"key":"2023080208561230100_c4","doi-asserted-by":"publisher","first-page":"207","DOI":"10.1038\/315207a0","volume":"315","year":"1985","journal-title":"Nature (London)"},{"key":"2023080208561230100_c5","doi-asserted-by":"crossref","first-page":"501","DOI":"10.1038\/376501a0","volume":"376","year":"1995","journal-title":"Nature (London)"},{"key":"2023080208561230100_c6","doi-asserted-by":"publisher","first-page":"569","DOI":"10.1038\/21164","volume":"399","year":"1999","journal-title":"Nature (London)"},{"key":"2023080208561230100_c7","doi-asserted-by":"crossref","first-page":"14501","DOI":"10.1029\/JD091iD13p14501","volume":"91","year":"1986","journal-title":"J. Geophys. Res."},{"key":"2023080208561230100_c8","doi-asserted-by":"publisher","first-page":"3708","DOI":"10.1063\/1.1679722","volume":"58","year":"1973","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c9","doi-asserted-by":"publisher","first-page":"4820","DOI":"10.1063\/1.1680987","volume":"60","year":"1974","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c10","doi-asserted-by":"publisher","first-page":"6290","DOI":"10.1063\/1.456345","volume":"90","year":"1989","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c11","doi-asserted-by":"publisher","first-page":"8333","DOI":"10.1063\/1.468098","volume":"101","year":"1994","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c12","doi-asserted-by":"publisher","first-page":"289","DOI":"10.1016\/0009-2614(93)89328-F","volume":"212","year":"1993","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c13","doi-asserted-by":"publisher","first-page":"7120","DOI":"10.1063\/1.466911","volume":"100","year":"1994","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c14","doi-asserted-by":"publisher","first-page":"1011","DOI":"10.1063\/1.466683","volume":"100","year":"1994","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c15","doi-asserted-by":"publisher","first-page":"1127","DOI":"10.1063\/1.445914","volume":"79","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c16","doi-asserted-by":"publisher","first-page":"1019","DOI":"10.1063\/1.444901","volume":"78","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c17","doi-asserted-by":"publisher","first-page":"7709","DOI":"10.1063\/1.473771","volume":"106","year":"1997","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c18","doi-asserted-by":"publisher","first-page":"7541","DOI":"10.1021\/jp9600470","volume":"100","year":"1996","journal-title":"J. Phys. Chem."},{"key":"2023080208561230100_c19","doi-asserted-by":"publisher","first-page":"233","DOI":"10.1146\/annurev.physchem.49.1.233","volume":"49","year":"1998","journal-title":"Annu. Rev. Phys. Chem."},{"key":"2023080208561230100_c20","first-page":"189","volume-title":"Methods of Electronic Structure Theory","author":"Schaefer","year":"1976"},{"key":"2023080208561230100_c21","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1002\/qua.560080106","volume":"8","year":"1974","journal-title":"Int. J. Quantum Chem."},{"key":"2023080208561230100_c22","doi-asserted-by":"publisher","first-page":"278","DOI":"10.1016\/0009-2614(80)80291-0","volume":"72","year":"1981","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c23","doi-asserted-by":"publisher","first-page":"481","DOI":"10.1016\/0009-2614(93)85670-J","volume":"214","year":"1993","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c24","doi-asserted-by":"publisher","first-page":"3600","DOI":"10.1063\/1.470243","volume":"103","year":"1995","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c25","doi-asserted-by":"publisher","first-page":"2067","DOI":"10.1039\/b000224k","volume":"2","year":"2000","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2023080208561230100_c26","doi-asserted-by":"publisher","first-page":"6288","DOI":"10.1021\/jp952840j","volume":"100","year":"1996","journal-title":"J. Phys. Chem."},{"key":"2023080208561230100_c27","doi-asserted-by":"publisher","first-page":"400","DOI":"10.1016\/0009-2614(96)00672-0","volume":"258","year":"1996","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c28","doi-asserted-by":"publisher","first-page":"2085","DOI":"10.1063\/1.462060","volume":"96","year":"1992","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c29","first-page":"345","volume-title":"Modern Electronic Structure Theory","author":"Yarkony","year":"1995"},{"key":"2023080208561230100_c30","doi-asserted-by":"publisher","first-page":"126","DOI":"10.1063\/1.465791","volume":"99","year":"1993","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c31","doi-asserted-by":"publisher","first-page":"2669","DOI":"10.1063\/1.459841","volume":"94","year":"1991","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c32","doi-asserted-by":"publisher","first-page":"720","DOI":"10.1063\/1.445820","volume":"79","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c33","doi-asserted-by":"publisher","first-page":"4858","DOI":"10.1063\/1.460571","volume":"94","year":"1990","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c34","doi-asserted-by":"crossref","first-page":"1004","DOI":"10.1007\/11424758_104","volume":"3480","year":"2005","journal-title":"Lect. Notes Comput. Sci."},{"key":"2023080208561230100_c35","doi-asserted-by":"publisher","first-page":"11614","DOI":"10.1063\/1.1807378","volume":"121","year":"2004","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c36","doi-asserted-by":"publisher","first-page":"189","DOI":"10.1016\/S0009-2614(03)01132-1","volume":"377","year":"2003","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c37","doi-asserted-by":"publisher","first-page":"1647","DOI":"10.1080\/00268970210155121","volume":"100","year":"2002","journal-title":"Mol. Phys."},{"key":"2023080208561230100_c38","doi-asserted-by":"publisher","first-page":"1007","DOI":"10.1063\/1.456153","volume":"90","year":"1989","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c39","doi-asserted-by":"publisher","first-page":"6796","DOI":"10.1063\/1.462569","volume":"96","year":"1992","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c40","doi-asserted-by":"publisher","first-page":"9244","DOI":"10.1063\/1.1367373","volume":"114","year":"2001","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c41","first-page":"91","volume":"15","year":"1981","journal-title":"Int. J. Quantum Chem., Quantum Chem. Symp."},{"key":"2023080208561230100_c42","first-page":"149","volume":"22","year":"1988","journal-title":"Int. J. Quantum Chem., Quantum Chem. Symp."},{"year":"2003","key":"2023080208561230100_c43"},{"key":"2023080208561230100_c44","doi-asserted-by":"publisher","first-page":"664","DOI":"10.1039\/B008063M","volume":"3","year":"2001","journal-title":"Phys. Chem. Chem. Phys."},{"year":"1997","key":"2023080208561230100_c45"},{"key":"2023080208561230100_c46","doi-asserted-by":"publisher","first-page":"8191","DOI":"10.1021\/ja00047a032","volume":"114","year":"1992","journal-title":"J. Am. Chem. Soc."},{"key":"2023080208561230100_c47","doi-asserted-by":"publisher","first-page":"31","DOI":"10.1016\/S0022-2860(84)87198-7","volume":"114","year":"1984","journal-title":"J. Mol. Struct."},{"key":"2023080208561230100_c48","doi-asserted-by":"publisher","first-page":"140","DOI":"10.1016\/S0009-2614(99)01187-2","volume":"3","year":"1969","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c49","doi-asserted-by":"publisher","first-page":"553","DOI":"10.1080\/00268977000101561","volume":"19","year":"1970","journal-title":"Mol. Phys."},{"key":"2023080208561230100_c50","doi-asserted-by":"publisher","first-page":"765","DOI":"10.1002\/jcc.1042","volume":"22","year":"2001","journal-title":"J. Comput. Chem."},{"key":"2023080208561230100_c51","doi-asserted-by":"publisher","first-page":"579","DOI":"10.1080\/00268977500102151","volume":"30","year":"1975","journal-title":"Mol. Phys."},{"key":"2023080208561230100_c52","doi-asserted-by":"publisher","first-page":"1311","DOI":"10.1063\/1.1673131","volume":"52","year":"1970","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c53","doi-asserted-by":"publisher","first-page":"763","DOI":"10.1080\/00268977400100661","volume":"27","year":"1974","journal-title":"Mol. Phys."},{"key":"2023080208561230100_c54","doi-asserted-by":"publisher","first-page":"169","DOI":"10.1016\/0009-2614(80)80629-4","volume":"76","year":"1980","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c55","doi-asserted-by":"publisher","first-page":"10768","DOI":"10.1021\/j100205a033","volume":"96","year":"1992","journal-title":"J. Phys. Chem."},{"key":"2023080208561230100_c56","doi-asserted-by":"publisher","first-page":"12764","DOI":"10.1021\/j100034a013","volume":"99","year":"1995","journal-title":"J. Phys. Chem."},{"key":"2023080208561230100_c57","doi-asserted-by":"crossref","first-page":"10430","DOI":"10.1021\/jp983453n","volume":"102","year":"1998","journal-title":"J. Phys. Chem."},{"volume-title":"Atomic Energy Levels","year":"1971","key":"2023080208561230100_c58"},{"key":"2023080208561230100_c59","doi-asserted-by":"publisher","first-page":"1860","DOI":"10.1063\/1.1740593","volume":"23","year":"1955","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c60","doi-asserted-by":"publisher","first-page":"2664","DOI":"10.1063\/1.448263","volume":"82","year":"1985","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c61","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1007\/978-1-4757-0887-5","volume-title":"Methods of Electronic Structure Theory","author":"Schaefer","year":"1977"},{"key":"2023080208561230100_c62","doi-asserted-by":"publisher","first-page":"3265","DOI":"10.1063\/1.447079","volume":"80","year":"1984","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c63","doi-asserted-by":"publisher","first-page":"1703","DOI":"10.1063\/1.444969","volume":"78","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c64","doi-asserted-by":"publisher","first-page":"6055","DOI":"10.1063\/1.449593","volume":"83","year":"1985","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c65","doi-asserted-by":"publisher","first-page":"7176","DOI":"10.1063\/1.478621","volume":"110","year":"1999","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c66","doi-asserted-by":"publisher","first-page":"1175","DOI":"10.1021\/jp0259014","volume":"107","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"2023080208561230100_c67","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/j.theochem.2005.12.007","volume":"760","year":"2006","journal-title":"J. Mol. Struct.: THEOCHEM"},{"key":"2023080208561230100_c68a","doi-asserted-by":"publisher","first-page":"3865","DOI":"10.1103\/PhysRevLett.77.3865","volume":"77","year":"1996","journal-title":"Phys. Rev. Lett."},{"key":"2023080208561230100_c68b","first-page":"1396","volume":"78","year":"1997","journal-title":"Phys. Rev. Lett."},{"volume-title":"Molecular Thermodynamics","year":"1999","key":"2023080208561230100_c69"},{"key":"2023080208561230100_c70","doi-asserted-by":"publisher","first-page":"6327","DOI":"10.1063\/1.1402167","volume":"115","year":"2001","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c71","doi-asserted-by":"publisher","first-page":"3510","DOI":"10.1063\/1.1532314","volume":"118","year":"2003","journal-title":"J. Chem. Phys."},{"first-page":"375","volume-title":"Photochemistry of Small Molecules","year":"1978","key":"2023080208561230100_c72"},{"key":"2023080208561230100_c73","doi-asserted-by":"publisher","first-page":"220","DOI":"10.1098\/rspa.1937.0142","volume":"161","year":"1937","journal-title":"Proc. R. Soc. London, Ser. A"},{"key":"2023080208561230100_c74","doi-asserted-by":"publisher","first-page":"243","DOI":"10.1016\/S0009-2614(98)00111-0","volume":"286","year":"1998","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c75","doi-asserted-by":"publisher","first-page":"45","DOI":"10.1016\/S0009-2614(98)00866-5","volume":"294","year":"1998","journal-title":"Chem. Phys. Lett."},{"key":"2023080208561230100_c76","doi-asserted-by":"publisher","first-page":"746","DOI":"10.1063\/1.1331107","volume":"114","year":"2001","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c77","doi-asserted-by":"publisher","first-page":"1702","DOI":"10.1063\/1.1532312","volume":"118","year":"2003","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c78","doi-asserted-by":"publisher","first-page":"7322","DOI":"10.1063\/1.1668615","volume":"120","year":"2004","journal-title":"J. Chem. Phys."},{"key":"2023080208561230100_c79","doi-asserted-by":"publisher","first-page":"7330","DOI":"10.1063\/1.1668631","volume":"120","year":"2004","journal-title":"J. Chem. Phys."}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/1.2800020\/15406528\/164320_1_online.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/1.2800020\/15406528\/164320_1_online.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,2]],"date-time":"2023-08-02T08:56:25Z","timestamp":1690966585000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/127\/16\/164320\/937306\/Dissociation-of-ground-and-n-states-of-CF3Cl-using"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2007,10,28]]},"references-count":80,"journal-issue":{"issue":"16","published-print":{"date-parts":[[2007,10,28]]}},"URL":"https:\/\/doi.org\/10.1063\/1.2800020","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"type":"print","value":"0021-9606"},{"type":"electronic","value":"1089-7690"}],"subject":[],"published-other":{"date-parts":[[2007,10,28]]},"published":{"date-parts":[[2007,10,28]]},"article-number":"164320"}}