{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:00:49Z","timestamp":1760266849903,"version":"3.41.2"},"reference-count":58,"publisher":"AIP Publishing","issue":"7","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2008,2,21]]},"abstract":"<jats:p>The polarized and depolarized Raman profiles of supercritical CO2 have been measured in the region of the \u03bd2 bending mode (forbidden transition at about 668cm\u22121) and for the Fermi dyad (1285 and 1388cm\u22121) along the isotherms 307, 309, 313, and 323K in a reduced density domain 0.04&amp;lt;\u03c1*=\u03c1\u2215\u03c1C&amp;lt;2.04 (\u03c1C\u223c467.6kgm\u22123, \u03c1C is the critical density). The spectral features associated with the \u03bd2 mode (degeneracy removal of the mode and Raman intensity activation) are found to be due to the formation of transient complexes. This is supported by the spectral signatures predicted for parallel slipped dimer and trimers (cyclic and noncyclic) from ab initio calculations taking into account the frequency anharmonicity. The band-shape analysis of the Fermi doublet (observed in the spectral range of 1260\u20131400cm\u22121) shows that on the subpicosecond time scale of the Raman spectroscopy, a tagged CO2 molecule probed two kinds of environment in its first shell of neighbors independent of local density enhancement phenomenon. The first one involves interactions of CO2 with surrounding molecules in the first shell whereas the latter is associated with a transient dimer formation. Finally, a broad band observed between the Fermi dyad (at about 1335cm\u22121) is assessed from symmetry considerations and from its depolarization ratio as a further evidence of transient complex formation in supercritical CO2.<\/jats:p>","DOI":"10.1063\/1.2833493","type":"journal-article","created":{"date-parts":[[2008,2,21]],"date-time":"2008-02-21T23:48:35Z","timestamp":1203637715000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":24,"title":["Transient dimer formation in supercritical carbon dioxide as seen from Raman scattering"],"prefix":"10.1063","volume":"128","author":[{"given":"M. Isabel","family":"Caba\u00e7o","sequence":"first","affiliation":[{"name":"Centro de F\u00edsica At\u00f3mica da UL 1 , Av. Prof. Gama Pinto 2, 1694-003 Lisboa, Portugal and Departamento de F\u00edsica, , UTL, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"},{"name":"Instituto Superior T\u00e9cnico 1 , Av. Prof. Gama Pinto 2, 1694-003 Lisboa, Portugal and Departamento de F\u00edsica, , UTL, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"given":"S.","family":"Longelin","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Bordeaux 1 2 Institut des Sciences Mol\u00e9culaires, CNRS (UMR 5255), , 351 Cours de la Lib\u00e9ration, 33405 Talence Cedex, France"}]},{"given":"Y.","family":"Danten","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Bordeaux 1 2 Institut des Sciences Mol\u00e9culaires, CNRS (UMR 5255), , 351 Cours de la Lib\u00e9ration, 33405 Talence Cedex, France"}]},{"given":"M.","family":"Besnard","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Bordeaux 1 2 Institut des Sciences Mol\u00e9culaires, CNRS (UMR 5255), , 351 Cours de la Lib\u00e9ration, 33405 Talence Cedex, France"}]}],"member":"317","published-online":{"date-parts":[[2008,2,21]]},"reference":[{"key":"2023080105171635200_c1","doi-asserted-by":"publisher","first-page":"3489","DOI":"10.1021\/j100297a007","volume":"91","year":"1987","journal-title":"J. Phys. 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