Vibrational spectra and normal coordinate analysis of CF 3 OF and CF 3 OCl
dc.contributor.author | Kuo, J. C. | en_US |
dc.contributor.author | Desmarteau, D. D. | en_US |
dc.contributor.author | Fateley, W. G. | en_US |
dc.contributor.author | Hammaker, R. M. | en_US |
dc.contributor.author | Marsden, C. J. | en_US |
dc.contributor.author | Witt, J. D. | en_US |
dc.date.accessioned | 2012-05-21T15:48:43Z | |
dc.date.available | 2012-05-21T15:48:43Z | |
dc.date.issued | 1980-08 | en_US |
dc.identifier.citation | Kuo, J. C.; Desmarteau, D. D.; Fateley, W. G.; Hammaker, R. M.; Marsden, C. J.; Witt, J. D. (1980). "Vibrational spectra and normal coordinate analysis of CF 3 OF and CF 3 OCl." Journal of Raman Spectroscopy 9(4): 230-238. <http://hdl.handle.net/2027.42/91176> | en_US |
dc.identifier.issn | 0377-0486 | en_US |
dc.identifier.issn | 1097-4555 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/91176 | |
dc.description.abstract | The IR spectra (1400 cm −1 to 160 cm −1 ) of the gases at ambient temperature and the Raman spectra (below 1400 cm −1 ) of the liquids near −196°C are reported for CF 3 OF and CF 3 OCl. All fundamentals are assigned under C s symmetry and the results of a normal coordinate analysis are presented. The assignments of Smardzewski and Fox are adopted with one exception for both CF 3 OF and CF 3 OCl: the CF 3 rock of A ″ symmetry is assigned near 430 cm −1 and the two bands between 200 cm −1 and 300 cm −1 are assigned to an A ′ fundamental, involving CF 3 rocking and COX bending and a Δ ν =2 transition in the CF 3 torsion. An extra band at 548 cm −1 in the Raman spectrum of liquid CF 3 COl near −196°C is assigned to a CF 3 OCl ⃛Cl 2 complex. The values of the force constants d (OX) for CF 3 OX molecules are suggested to be near those for X 2 O molecules. More than half the normal modes of A ′ symmetry show extensive mixing of symmetry coordinates. In some of these cases the symmetry coordinate for which the normal mode is named is the largest but not the dominant contributor to the potential energy distribution, while in others this symmetry coordinate is not even the largest contributor to the potential energy distribution. No normal modes of A ′ symmetry are present in which ν(CO), δ s (CF 3 ), δ(COX), or δ(CF 3 ) symmetry coordinates are dominant, and the mode conventionally labeled as v (CO) should be labeled as ν s (CF 3 ). For the remaining A ′ normal modes and all the A ″ normal modes, the symmetry coordinate for which the normal mode is named is dominant in the potential energy distribution. | en_US |
dc.publisher | John Wiley & Sons, Ltd. | en_US |
dc.title | Vibrational spectra and normal coordinate analysis of CF 3 OF and CF 3 OCl | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Biological Chemistry | en_US |
dc.subject.hlbsecondlevel | Chemistry | en_US |
dc.subject.hlbsecondlevel | Physics | en_US |
dc.subject.hlbtoplevel | Health Sciences | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA | en_US |
dc.contributor.affiliationother | IBM Corporation, Tucson, Arizona, USA | en_US |
dc.contributor.affiliationother | Department of Chemistry, Melbourne University, Parkville, Victoria 3052, Australia | en_US |
dc.contributor.affiliationother | Corporate Chemical Research Laboratory, Allied Chemical Company, Morristown, New Jersey 07960, USA | en_US |
dc.contributor.affiliationother | Department of Chemistry, Kansas State University, Manhattan, Kansas 66506, USA | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/91176/1/1250090406_ftp.pdf | |
dc.identifier.doi | 10.1002/jrs.1250090406 | en_US |
dc.identifier.source | Journal of Raman Spectroscopy | en_US |
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dc.identifier.citedreference | Since low temperature should favor complex formation, the complex is probably not present in the gaseous CF 3 OCl at room temperature. Even if the complex were present in the gas it would probably be too weak to cause the IR inactive stretching of gaseous Cl 2 to become observable in the IR spectrum of the gaseous complex. Thus, the absence of a 548 cm −1 band in the IR spectrum of gaseous CF 3 OCl at room temperature is consistent with the presence of a weak CF 3 OClClCl complex at low temperature. | en_US |
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dc.identifier.citedreference | For CF 3 OX the structural parameters are the CF, CO and OX bond lengths and the five angles: FCF angle or α, tilt angle or β, COX angle or γ, the angle each CF bond makes with the C, 3 axis of the CF 3 group of δ, and the FCO angle for the F atom in the FCOX plane or θ. Specification of α and β fixes the angles δ and θ since only two of the four angles α, β, δ and θ are independent. The angle of tilt, β, is in the FCOX plane between the C, 3 axis of the CF 3 group and the C—O bond. For a positive angle of tilt the F atom in the FCOX plane is closer to the O atom than are the two out‐of‐plane F atoms. The following structural parameters were used for both CF 3 OF and CF 3 OCl: R(C—F)= 1.319 Å, R(C—O)= 1.395 Å, α = 109.4°, β = 4.1°, δ = 70.5°, θ = 105.4°. For CF 3 OF, R(O—F) = 1.421 Å, and γ = 104.8°. For CF 3 OCl, R(O—Cl) = 1.70° and γ = 112.8°. These two parameters were estimated by comparison of CF 3 OF with F 2 O 31 and F 2 O 31 with Cl 2 O 31. Since the OF bonds in CF 3 OF and F 2 O differ by only about 0.01 Å, the O—Cl bond length from Cl 2 O is used for CF 3 OCl. Since the Cl—O—Cl angle in Cl 2 O is 8° larger than the F—O—F angle in F 2 O, the Cl—O—Cl angle in CF 3 OCl is taken as 8° larger than the C—O—F angle in CF 3 OF. The principal moments of inertia for CF 3 OF in amu‐Å 2 are 89.6, 164.6 and 166.0 and the asymmetry parameter is −0.98. The principal moments of inertia for CF 3 OCl in amu‐Å 2 are 89.6, 254.9 and 256.4 and the asymmetry parameter is −0.99. The α, β, γ and δ used in this note are defined in Fig. 1 of Ref. 5 and do not correspond to the angles defined in our Fig. 3 in all cases. | en_US |
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dc.identifier.citedreference | The mixing of CF 3 group modes with modes of the remainder of the molecule has been reported previously.See for example, E. C. Tuazon, W. G. Fateley and F. F. Bentley, Appl. Spectrosc., 25, 374 ( 1971 ). | en_US |
dc.identifier.citedreference | See Table 15 in Ref. 18. | en_US |
dc.identifier.citedreference | A symmetry coordinate is classified as making the dominant contribution to a column in Table 5 if the corresponding entry is greater than 67% of the sum of the entries in that column or if the corresponding entry is a factor of 4 or more larger than the next largest entry in that column. | en_US |
dc.identifier.citedreference | The normal modes in the A ′ block that have reasonable symbols in Table 1 are: CF 3 OF, v, as (CF 3 ) A ′, v,(OF) A ′ and δ as ( CF, 3 ) A ′; CF 3 OCl, v, as (CF 3 ) A ′ and δ as (CF 3 ) A ′. | en_US |
dc.identifier.citedreference | The normal mode symbols where the symmetry coordinate for which the normal modes is named makes the largest but not the dominant contribution are: CF 3 OF, δ s (CF 3 ) A ′, and ρ(CF 3 ) A ′; CF 3 OCl, v,(OCl) A ′ and δ(CF 3 ) A ′. | en_US |
dc.identifier.citedreference | The normal mode symbols where another symmetry coordinate makes the largest contribution are: CF 3 OF, v, s (CF 3 ) A ′, v,(CO) A ′ and δ(COF) A ′; CF 3 OCl, v, s (CF 3 ) A ′, v,(CO) A ′; δ(COCl) A ′ and ρ(CF 3 ) A ′. | en_US |
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dc.identifier.citedreference | Ajit S. Manocha, MS Thesis,Kansas State University, Manhattan, KS USA( 1978 ). | en_US |
dc.identifier.citedreference | A. S. Manocha, D. D. DesMarteau, R. M. Hammaker and C. J. Marsden,in preparation. | en_US |
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dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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