Coupled Cluster and Density Functional Theory Studies of the Vibrational Contribution to the Optical Rotation of (S)-Propylene Oxide.
In a previous study (Chemical Physics Letters2005, 401 ,385) we computed the optical rotatory dispersion of (S)-propylene oxide in gas phase and solution using the hierarchy of coupled cluster models CCS, CC2, CCSD, and CC3. Even for the highly correlated CC3 model combined with a flexible basis set...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 3; pp. 976 - 983 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
1/25/2006
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=20217835&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 20217835 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 1/25/2006 vid: 128 iid: 3 pid: 997 pub: American Chemical Society artinfo: ui: 20217835 10.1021/ja056611e ppf: 976 ppct: 7 formats: tig: atl: Coupled Cluster and Density Functional Theory Studies of the Vibrational Contribution to the Optical Rotation of (S)-Propylene Oxide. aug: au: Jacob Kongsted Thomas Bondo Pedersen Lasse Jensen Aage E. Hansen Kurt V. Mikkeisen affil: Contribution from the Department of Chemistry, University of Aarhus, Langelandsgade 140, DK-8000 Aarhus C, Denmark Department of Theoretical Chemistry, Chemical Center, University of Lund, P.O. Box 124, S-22 1 00 Lund, Sweden Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113 Department of Chemistry, H. C. ∅rsted Institute, University of Copenhagen, DK-2 100 Copenhagen Ø, Denmark su: Propylene oxide Density functionals Optical polarization Dispersion (Chemistry) Molecular rotation Biochemistry sug: subj: Propylene oxide Density functionals Optical polarization Dispersion (Chemistry) Molecular rotation Biochemistry ab: In a previous study (Chemical Physics Letters2005, 401 ,385) we computed the optical rotatory dispersion of (S)-propylene oxide in gas phase and solution using the hierarchy of coupled cluster models CCS, CC2, CCSD, and CC3. Even for the highly correlated CC3 model combined with a flexible basis set, the theoretical gas-phase specific rotation at 355 nm was found to be negative in contrast to the experimental result. We argued that vibrational contributions could be crucial for obtaining a complete understanding of the experimental result. Here, we show that this indeed is the case by using coupled cluster models and density functional theory methods to calculate the vibrational contributions to the gas-phase specific rotation at 355, 589.3, and 633 nm. While density functional theory (B3LYP and SAOP functionals) overestimates the specific rotation at 355 nm by approximately 1 order of magnitude and yields an incorrect sign at 589.3 and 633 nm, the coupled cluster results are in excellent agreement with the experimentally measured optical rotations. We find that all vibrational modes contribute significantly to the optical rotation and that temperature effects must be taken into account. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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