Evidence for Pseudo‐Jahn—Teller Effect in XeF6
dc.contributor.author | Bartell, Lawrence S. | en_US |
dc.date.accessioned | 2010-05-06T22:30:08Z | |
dc.date.available | 2010-05-06T22:30:08Z | |
dc.date.issued | 1967-06-01 | en_US |
dc.identifier.citation | Bartell, L. S. (1967). "Evidence for Pseudo‐Jahn—Teller Effect in XeF6." The Journal of Chemical Physics 46(11): 4530-4531. <http://hdl.handle.net/2027.42/70654> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/70654 | |
dc.format.extent | 3102 bytes | |
dc.format.extent | 199987 bytes | |
dc.format.mimetype | text/plain | |
dc.format.mimetype | application/pdf | |
dc.publisher | The American Institute of Physics | en_US |
dc.rights | © The American Institute of Physics | en_US |
dc.title | Evidence for Pseudo‐Jahn—Teller Effect in XeF6 | en_US |
dc.type | Article | en_US |
dc.subject.hlbsecondlevel | Physics | 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 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/70654/2/JCPSA6-46-11-4530-1.pdf | |
dc.identifier.doi | 10.1063/1.1840580 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
dc.identifier.citedreference | Brevity precludes a discussion of alternative interpretations. It also precludes a resumé of all relevant data. | en_US |
dc.identifier.citedreference | N. V. Sidgwick and H. M. Powell, Proc. Roy. Soc. (London) A176, 153 (1940); R. J. Gillespie and R. S. Nyholm, Quart. Rev. (London) 11, 339 (1957). R. J. Gillespie, Noble Gas Compounds (University of Chicago Press, Chicago, Ill., 1963), p. 333. | en_US |
dc.identifier.citedreference | R. J. Gillespie, J. Chem. Ed. 40, 295 (1963). | en_US |
dc.identifier.citedreference | L. S. Bartell, Trans. Am. Cryst. Assoc. 2, 134 (1966); Inorg. Chem. 5, 1635 (1966). | en_US |
dc.identifier.citedreference | B. J. Nicholson (private communication, December, 1966). | en_US |
dc.identifier.citedreference | L. Lohr (private communication, January, 1967). | en_US |
dc.identifier.citedreference | R. M. Gavin, Jr., and L. S. Bartell (unpublished). | en_US |
dc.identifier.citedreference | L. S. Bartell, R. M. Gavin, Jr., H. B. Thompson, and C. L. Chernick, J. Chem. Phys. 43, 2547 (1965). | en_US |
dc.identifier.citedreference | K. Hedberg, S. H. Peterson, R. R. Ryan, and B. Weinstock, J. Chem. Phys. 44, 1726 (1966). | en_US |
dc.identifier.citedreference | L. S. Bartell and R M Gavin, Jr. (unpublished). | en_US |
dc.identifier.citedreference | U. Öpik and M. H. L. Pryce, Proc. Roy. Soc. (London) A238, 425 (1957); D. M. W. Den Boer, P. C. Den Boer, and H. C. Longuet‐Higgins, Mol. Phys. 5, 387 (1962); B. J. Nicholson and H. C. Longuet‐Higgins, 9, 461 (1965). By pseudo‐Jahn‐Teller effect we imply (following Longuet‐Higgins) that in cases where low‐lying excited states can mix heavily with the ground state when a distortion occurs, the distortion may become energetically favorable. For octahedral XeF6XeF6 the ground state is, presumably, A1gA1g and the lowest excited state is T1u.T1u. Accordingly, the t1u.t1u. force constants will tend to be low or, indeed, negative if the interaction is strong enough to qualify as a pseudo-Jahn-Teller interaction. Note that since an analogous destabilization of symmetrical configurations formally applies to all XYm(e2)nXYm(e2)n molecules with stereochemically active Gillespie lone pairs the above definition of pseudo-Jahn-Teller effect is not very restrictive. | en_US |
dc.identifier.citedreference | For a definition of these coordinates see C. W. F. T. Pistorius, J. Chem. Phys. 29, 1328 (1958) but note that S4d,S4d, S4b,S4b, and S4cS4c of the present paper correspond to R1b,R1b, R2b,R2b, and R3bR3b of Pistorius. For a graphic portrayal of t1ut1u bends leading to C2υC2υ and C3υ,C3υ, structure, see Ref. 4(a). The fact that the inversion coordinates are not pure bends is strongly indicated by Conclusion (4) of the text and by the abnormally large amplitudes of the XeF bonds. | en_US |
dc.identifier.citedreference | This magnitude implies atomic displacements of 0.3 Å for a pure t1ut1u distortion to C3νC3ν symmetry. | en_US |
dc.identifier.citedreference | The observed correlation between the t1ut1u mode and t2gt2g impurity mode (and to as lesser extent, the egeg impurity mode) is in the direction of relieving the compression between backside ligands when the frontside ligands adjacent to the lone pair are spread apart. | en_US |
dc.identifier.citedreference | The author is indebted to Dr. H. H. Claassen and Dr. E. L. Gasner for unpublished information on the Raman spectrum showing that the stretching bands actually exhibit coincidences with the infrared (private communication, January 1967, prior to assignment scheme described in text). | en_US |
dc.identifier.citedreference | B. Weinstock, E. E. Weaver, and C. P. Knop, Inorg. Chem. 5, 2189 (1966). | en_US |
dc.identifier.citedreference | W. E. Falconer, A. Buchler, J. L. Stauffer, and W. Klemperer (unpublished). | en_US |
dc.owningcollname | Physics, Department of |
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