Vibrational spectroscopy of 1,1-difluorocyclopropane-d0, -d2, and -d4: The equilibrium structure of difluorocyclopropane

Title:
Vibrational spectroscopy of 1,1-difluorocyclopropane-d0, -d2, and -d4: The equilibrium structure of difluorocyclopropane
Authors:
Craig, Norman C.; Feller, David; Groner, Peter; Hsin, Hong Yuan; McKean, Donald C.; Nemchick, Deacon J.
Abstract:
IR and Raman spectra are reported for 1,1-difluorocyclopropane-d0, -d2, and -d4, and complete assignments of vibrational fundamentals are given for these species. These assignments are consistent with predictions of frequencies, intensities, and Raman depolarization ratios computed with the B3LYP/cc-pVTZ quantum chemical (QC) model. Ground state rotational constants for five 13C and deuterium isotopomers, obtained from published microwave spectra, were “corrected” into equilibrium rotational constants. The needed vibration−rotation interaction constants were computed with QC models after scaling the force constants. A semi-experimental equilibrium structure, fitted to the equilibrium moments of inertia, is rC1C = 1.470(1) Å, rCC = 1.546(1) Å, rCF = 1.343(1) Å, rCH = 1.078(1) Å, αFCF = 109.5(1), αFCC = 119.4(1)°, αHCH = 116.7(1)°, αC1CH = 117.4(1)°, and αCCH = 117.1(1)°. This structure agrees within the indicated uncertainties with the ab initio structure obtained from an extrapolated set of CCSD(T)/aug-cc-pVnZ calculations except for rCC = 1.548 Å. The F2C−CH2 bonds are significantly shortened and strengthened; the H2C−CH2 bond is significantly lengthened and weakened.
Citation:
Craig, Norman C., David Feller, Peter Groner, Hong Yuan Hsin, Donald C. McKean, and Deacon J. Nemchick. 2007. "Vibrational spectroscopy of 1,1-difluorocyclopropane-d0, -d2, and -d4: The equilibrium structure of difluorocyclopropane." Journal of Physical Chemistry A 111(13): 2498-2506.
Publisher:
American Chemical Society
DATE ISSUED:
2007
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1021/jp0686947
PERMANENT LINK:
http://hdl.handle.net/11282/334130

Full metadata record

DC FieldValue Language
dc.contributor.authorCraig, Norman C.en
dc.contributor.authorFeller, Daviden
dc.contributor.authorGroner, Peteren
dc.contributor.authorHsin, Hong Yuanen
dc.contributor.authorMcKean, Donald C.en
dc.contributor.authorNemchick, Deacon J.en
dc.date.accessioned2014-11-10T14:14:20Z-
dc.date.available2014-11-10T14:14:20Z-
dc.date.issued2007en
dc.identifier.citationCraig, Norman C., David Feller, Peter Groner, Hong Yuan Hsin, Donald C. McKean, and Deacon J. Nemchick. 2007. "Vibrational spectroscopy of 1,1-difluorocyclopropane-d0, -d2, and -d4: The equilibrium structure of difluorocyclopropane." Journal of Physical Chemistry A 111(13): 2498-2506.en
dc.identifier.issn1089-5639en
dc.identifier.urihttp://hdl.handle.net/11282/334130-
dc.description.abstractIR and Raman spectra are reported for 1,1-difluorocyclopropane-d0, -d2, and -d4, and complete assignments of vibrational fundamentals are given for these species. These assignments are consistent with predictions of frequencies, intensities, and Raman depolarization ratios computed with the B3LYP/cc-pVTZ quantum chemical (QC) model. Ground state rotational constants for five 13C and deuterium isotopomers, obtained from published microwave spectra, were “corrected” into equilibrium rotational constants. The needed vibration−rotation interaction constants were computed with QC models after scaling the force constants. A semi-experimental equilibrium structure, fitted to the equilibrium moments of inertia, is rC1C = 1.470(1) Å, rCC = 1.546(1) Å, rCF = 1.343(1) Å, rCH = 1.078(1) Å, αFCF = 109.5(1), αFCC = 119.4(1)°, αHCH = 116.7(1)°, αC1CH = 117.4(1)°, and αCCH = 117.1(1)°. This structure agrees within the indicated uncertainties with the ab initio structure obtained from an extrapolated set of CCSD(T)/aug-cc-pVnZ calculations except for rCC = 1.548 Å. The F2C−CH2 bonds are significantly shortened and strengthened; the H2C−CH2 bond is significantly lengthened and weakened.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/jp0686947en
dc.subject.departmentChemistryen
dc.titleVibrational spectroscopy of 1,1-difluorocyclopropane-d0, -d2, and -d4: The equilibrium structure of difluorocyclopropaneen
dc.typeArticleen
dc.identifier.journalJournal of Physical Chemistry Aen
dc.identifier.volume111en
dc.identifier.issue13en
dc.identifier.startpage2498en
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