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Electron diffraction studies of hot molecules. I. Observed and calculated thermal expansions of SF6, CF4, and SiF4
dc.contributor.authorGoates, Steven R.en_US
dc.contributor.authorBartell, Lawrence S.en_US
dc.date.accessioned2010-05-06T21:28:20Z
dc.date.available2010-05-06T21:28:20Z
dc.date.issued1982-08-15en_US
dc.identifier.citationGoates, Steven R.; Bartell, Lawrence S. (1982). "Electron diffraction studies of hot molecules. I. Observed and calculated thermal expansions of SF6, CF4, and SiF4." The Journal of Chemical Physics 77(4): 1866-1873. <http://hdl.handle.net/2027.42/69996>en_US
dc.identifier.urihttps://hdl.handle.net/2027.42/69996
dc.description.abstractA new method is described for the rapid heating (10−5–10−6 s) of gas molecules for study by electron diffraction. Laser irradiation of the tip of a micronozzle makes it possible to determine structures, amplitudes of vibrations, and aspects of anharmonicity of molecules at temperatures much higher than those at which decomposition occurs in conventional oven nozzles. The vibrations and thermal expansions of SF6, CF4, and SiF4 have been investigated up to 1700, 1600, and 1200 K, respectively. Clear evidence for effects of anharmonicity was observed in amplitudes of vibration as well as mean bond lengths. Various models proposed for the treatment of increases in bond length have been assessed, among which an anharmonic Urey–Bradley field accounted well for results. Comparisons are made with the predictions of Heenan and Robiette based on spectroscopic analyses. The diffraction approach offers a promising method for augmenting spectroscopy in the investigation of intramolecular forces.en_US
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dc.publisherThe American Institute of Physicsen_US
dc.rights© The American Institute of Physicsen_US
dc.titleElectron diffraction studies of hot molecules. I. Observed and calculated thermal expansions of SF6, CF4, and SiF4en_US
dc.typeArticleen_US
dc.subject.hlbsecondlevelPhysicsen_US
dc.subject.hlbtoplevelScienceen_US
dc.description.peerreviewedPeer Revieweden_US
dc.contributor.affiliationumDepartment of Chemistry, University of Michigan, Ann Arbor, Michigan 48109en_US
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/69996/2/JCPSA6-77-4-1866-1.pdf
dc.identifier.doi10.1063/1.444038en_US
dc.identifier.sourceThe Journal of Chemical Physicsen_US
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dc.identifier.citedreferenceS. R. Goates and L. S. Bartell, J. Chem. Phys. 77, 1874 (1982).en_US
dc.identifier.citedreferenceS. R. Goates, Ph.D. thesis, University of Michigan, 1981.en_US
dc.identifier.citedreferenceSee AIP document No. PAPS JCPSA‐1866‐14 for 14 pages of related materials including conditions under which the diffraction plates were taken, representative intensities and derived results. Order by PAPS number and journal reference from American Institute of Physics, Physics Auxiliary Publication Service, 335 E. 45 St., New York, NY 10017. The price is $1.50 for each microfiche (98 pages), or $5 for photocopies of up to 30 pages and $0.15 for each page over 30 pages. Airmail is additional. Make checks payable to American Institute of Physics.en_US
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dc.identifier.citedreferenceThis is especially true when absorbances are small, as they were for the first 18 SF6SF6 plates and all CF4CF4 plates.en_US
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dc.identifier.citedreferenceBecause there is much confusion in the literature about the asymmetry constant used in electron diffraction, we shall designate by a the Morse potential constant, which is independent of temperature, and by âa, the temperature‐dependent asymmetry parameter related to the frequency modulation of intensity by the relation k  =  âl4/6.k=âl4∕6.en_US
dc.identifier.citedreferenceFor a discussion of shrinkage, see S. J. Cyvin, Molecular Vibrations and Mean Square Amplitudes (Elsevier, Amsterdam, 1968), see also Ref. 4.en_US
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dc.identifier.citedreferenceSee, for example, Ref. 17, and the citations therein.en_US
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dc.identifier.citedreferenceD. R. Herschbach and V. W. Laurie, J. Chem. Phys. 35, 458 (1961). In the case of SF6SF6 a value of a  =  1.6 Å−1a=1.6Å−1 was adopted, arbitrarily, following Ref. 15, instead of using the Herschbach and Laurie value of 1.8 Å−1.Å−1.en_US
dc.identifier.citedreferenceSee, for example, K. Kuchitsu and L. S. Bartell, J. Chem. Phys. 36, 2470 (1962); I. M. Mills, J. Phys. Chem. 80, 1187 (1976).en_US
dc.identifier.citedreferenceR. L. Hilderbrandt and D. A. Kohl, Theochem. 2, 25 (1981); D. A. Kohl and R. L. Hilderbrandt, 2, 325 (1981).en_US
dc.identifier.citedreferenceR. Heenan, Ph.D. thesis, University of Reading, England, 1979.en_US
dc.identifier.citedreferenceL. S. Bartell, J. Chem. Phys. 70, 4581 (1979).en_US
dc.identifier.citedreferenceL. S. Bartell and K. Kuchitsu, J. Chem. Phys. 37, 691 (1962). See also the first reference in Ref. 31.en_US
dc.identifier.citedreferenceJ. Hiraishi, I. Nakagawa, and T. Shimanouchi, Spectrochim. Acta 20, 819 (1964).en_US
dc.identifier.citedreferenceL. S. Bartell and S. E. Woehler (unpublished). The calculations yielded 149 exp(−3.75q)exp(−3.75q) for VFF(q)VFF(q) in mdyn Å, where q is the separation of fluorine atoms in Å. A brlef description of the calculations is given in Ref. 3.en_US
dc.identifier.citedreferenceR. S. McDowell, J. P. Aldridge, and R. F. Holland, J. Phys. Chem. 80, 1203 (1976).en_US
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dc.identifier.citedreferenceW. B. Person and K. C. Kim, J. Chem. Phys. 69, 2117 (1978).en_US
dc.identifier.citedreferenceSee M. J. Rothman, L. S. Bartell, C. S. Ewig, and J. R. Van Wazer, J. Chem. Phys. 73, 375 (1980); L. S. Bartell, A. Gavezzotti, and M. J. Rothman, 76, 4136 (1982); L. S. Bernstein and M. F. Vernon (unpublished).en_US
dc.identifier.citedreferenceIn the sense of “Valence‐Shell‐Electron‐Pair‐Repulsions,” discussed in Ref. 4.en_US
dc.owningcollnamePhysics, Department of


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