{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,20]],"date-time":"2026-03-20T12:24:10Z","timestamp":1774009450547,"version":"3.50.1"},"reference-count":29,"publisher":"AIP Publishing","issue":"11","funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["24-23-00194"],"award-info":[{"award-number":["24-23-00194"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]},{"name":"State assignment to A. M. Obukhov Institute of Atmospheric Physics, RAS","award":["125020501413-6"],"award-info":[{"award-number":["125020501413-6"]}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2026,3,21]]},"abstract":"<jats:p>The vibrational parity of a centrosymmetric molecule can be broken in the Raman spectra when the electric-dipole (E1) virtual transitions are accompanied by the electric-quadrupole (E2) or magnetic-dipole (M1) ones. To assess the intensity of the not yet detected \u03bd2 CO2 Raman band, accurate ab\u00a0initio values of the mixed E1\u2013E2 (A\u0302) and E1\u2013M1 (G\u0302) polarizabilities of a bent CO2 molecule are presently obtained using the DALTON program suite. The previous SCF results of Amos, Buckingham, and Williams [Mol. Phys. 39, 819 (1980)] for the A\u0302-tensor components are substantially refined by employing the extended basis sets and accounting for the electron correlation (up to CCSD). By using the SOPPA approach, the derivatives of G\u0302 are obtained for the first time. The results are processed to derive the rank-r irreducible spherical tensors (IST), X\u03ba(r), which vary in space as the Wigner functions D\u03bam(r) whose subscript \u03ba determines the dependence on the bent-molecule plane orientation relative to the symmetry axis. As a result, four ISTs (A1\u2009(1), A1\u2009(2), A1\u2009(3), and A3\u2009(3)) fully determine the \u03bd2 E1-E2 intensity whereas tensors G1\u2009(1) and G1\u2009(2) do the same for the magnetic channel. Using the thus derived properties, the integrated \u03bd2 band intensities are calculated for the first time and, like our recent assessments for the \u03bd3 band [Kouzov et\u00a0al., Opt. Spectrosc. 133, 581 (2025)], show the leading role of the E1\u2013M1 terms. The results could be helpful for detection of this novel parity-changing Raman process.<\/jats:p>","DOI":"10.1063\/5.0312738","type":"journal-article","created":{"date-parts":[[2026,3,20]],"date-time":"2026-03-20T10:27:14Z","timestamp":1774002434000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Ab initio mixed polarizabilities responsible for the Raman-forbidden\n                    <i>\u03bd<\/i>\n                    2 transition in carbon dioxide molecule"],"prefix":"10.1063","volume":"164","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4730-8841","authenticated-orcid":false,"given":"A. A.","family":"Finenko","sequence":"first","affiliation":[{"name":"Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences 1 , Pyzhevsky Lane, 3, Moscow 119017,","place":["Russia"]},{"name":"Department of Chemistry, Lomonosov Moscow State University 2 , GSP-1, Leninskiye Gory, 1-3, Moscow 119991,","place":["Russia"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1163-3359","authenticated-orcid":false,"given":"D. N.","family":"Chistikov","sequence":"additional","affiliation":[{"name":"Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences 1 , Pyzhevsky Lane, 3, Moscow 119017,","place":["Russia"]},{"name":"Institute of Quantum Physics, Irkutsk National Research Technical University 3 , Irkutsk 664074,","place":["Russia"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9035-8916","authenticated-orcid":false,"given":"A. P.","family":"Kouzov","sequence":"additional","affiliation":[{"name":"Saint-Petersburg State University 4 , Universitetskaya Emb., 7\/9, Saint Petersburg 199034,","place":["Russia"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2026,3,20]]},"reference":[{"key":"2026032006270848500_c1","doi-asserted-by":"publisher","first-page":"413","DOI":"10.1103\/PhysRev.71.413","volume":"71","year":"1947","journal-title":"Phys. Rev."},{"key":"2026032006270848500_c2","doi-asserted-by":"publisher","first-page":"170","DOI":"10.1038\/163170a0","volume":"163","year":"1949","journal-title":"Nature"},{"key":"2026032006270848500_c3","doi-asserted-by":"publisher","first-page":"77","DOI":"10.1029\/GL008i001p00077","volume":"8","year":"1981","journal-title":"Geophys. Res. Lett."},{"key":"2026032006270848500_c4","doi-asserted-by":"publisher","first-page":"2182","DOI":"10.1364\/ao.20.002182","volume":"20","year":"1981","journal-title":"Appl. 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