Vibrational Spectroscopy of the Three Isomers of 1,4-Difluorobutadiene

Norman C. Craig*, Christopher F. Neese, Tuan N. Nguyen, Catherine M. Oertel, Laura Pedraza, Anne M. Chaka

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    15 Scopus citations

    Abstract

    Infrared and Roman spectra were recorded for the trans.trans (EE), cis,cis (ZZ), and cis,trans (ZE) isomers of 1,4-difluorobutadiene (DFBD). From these spectra and frequencies predicted from the adiabatic connection method, which is a hybrid of Hartree-Fock and density-functional theories, complete assignments of fundamentals were made for the observable s-trans configurations. The fundamentals for the trans,trans isomer are (in cm-1): (ag) 3091, 3048, 1681, 1325, 1280, 1151, 1121, 409, 383; (au) 934, 798, 227, 154; (bg) 897, 830, 397; and (bu) 3086, 3056, 1638, 1299, 1221,1088, 621, 133. The fundamentals for the cis.cis isomer are (in cm-1): (ag) 3118, 3088, 1676, 1410, 1248, 1134, 946, 751, 232; (ag) 914, 762, 330, 78; (bg) 897, 789, 580; and (bu) 3109, 3092, 1624, 1340, 1215, 1044, 632, 165. The fundamentals for the cis,trans isomer are (in cm-1): (a′) 3114, 3082, 3062, 3036, 1690, 1629, 1391, 1313, 1253, 1224, 1138, 1129, 1008, 706, 504, 308, 138; and (a″) 929, 887, 824, 758, 526 (calculated), 230, 155. Overall agreement between the assignments and the predicted frequencies is quite good. With allowance for the difference between modes strongly dependent on CF or CCI motions, a very good correlation was found between the fundamentals of the three isomers of DFBD and the corresponding isomers of 1,4-dichlorobutadiene. Both sets of isomers are of special interest because they exhibit the cis effect, in which the cis,cis isomer has the lowest energy and the trans,-trans isomer has the highest energy.

    Original languageEnglish (US)
    Pages (from-to)6726-6739
    Number of pages14
    JournalJournal of Physical Chemistry A
    Volume103
    Issue number34
    DOIs
    StatePublished - Aug 26 1999

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Fingerprint Dive into the research topics of 'Vibrational Spectroscopy of the Three Isomers of 1,4-Difluorobutadiene'. Together they form a unique fingerprint.

    Cite this