Comparison of Molecular Structures Determined by Electron Diffraction and Spectroscopy. Ethane and Diborane
dc.contributor.author | Kuchitsu, Kozo | en_US |
dc.date.accessioned | 2010-05-06T22:03:29Z | |
dc.date.available | 2010-05-06T22:03:29Z | |
dc.date.issued | 1968-11-15 | en_US |
dc.identifier.citation | Kuchitsu, Kozo (1968). "Comparison of Molecular Structures Determined by Electron Diffraction and Spectroscopy. Ethane and Diborane." The Journal of Chemical Physics 49(10): 4456-4462. <http://hdl.handle.net/2027.42/70372> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/70372 | |
dc.description.abstract | Gas‐phase average structures for the ground‐vibrational state (rz)(rz) for ethane and diborane have been determined by a critical comparison of the experimental results obtained from electron diffraction (average internuclear distances rgrg) and those obtained from high‐resolution infrared and Raman spectroscopy (rotational constants Bz(α)Bz(α)). Experimental values have been taken from the recent literature and converted into the average structure (rzorrα0)(rzorrα0). The rgrg and rα0rα0 distances determined from electron diffraction carry uncertainties less than those in the rzrz distances determined from rotational constants, because the latter structures are very sensitive to assumptions about the unknown isotope differences in the structures. On the other hand, the average moments of inertia from spectroscopy are much more precise than those calculated from diffraction internuclear distances. Examinations of the data have led to the following rzrz structures with standard errors: For C2H6, rz(C�H)=1.0957±0.002Å,rz(C�C)=1.5319±0.002Å,and∠C�C�H=111.5°±0.3°; for C2D6, rz(C�D)=1.0941±0.002Å,rz(C�C)=1.5300±0.002Å,and∠C�C�D=111.4°±0.3°; and for B2H6, rz(B�Ht)=1.192±0.01Å,rz(B�Hb)=1.329±0.005Å,rz(B�B)=1.770±0.005Å, ∠Ht�B�Ht=121.8°±3°,and∠Hb�B�Hb=96.5°±0.5°. It was possible to increase the resolving power of the diffraction analysis of diborane by inclusion of calculated B☒H mean amplitudes.The effective complementary use of electron‐diffraction and spectroscopic data for determining reliable gas‐phase structures and the relative merits of the two alternative representations of the average structure (rgandrz)(rgandrz) have been discussed. | en_US |
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dc.format.extent | 551396 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 | Comparison of Molecular Structures Determined by Electron Diffraction and Spectroscopy. Ethane and Diborane | 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 48104 | en_US |
dc.contributor.affiliationother | Department of Chemistry, Faculty of Science, The University of Tokyo, Bunkyo‐ku, Tokyo, Japan | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/70372/2/JCPSA6-49-10-4456-1.pdf | |
dc.identifier.doi | 10.1063/1.1669897 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
dc.identifier.citedreference | Y. Morino, K. Kuchitsu, and T. Oka, J. Chem. Phys. 36, 1108 (1962). | en_US |
dc.identifier.citedreference | T. Oka, J. Phys. Soc. Japan 15, 2274 (1960). | en_US |
dc.identifier.citedreference | (a) D. R. Herschbach and V. W. Laurie, J. Chem. Phys. 37, 1668 (1962). (b) V. W. Laurie and D. R. Herschbach, J. Chem. Phys. 37, 1687 (1962). | en_US |
dc.identifier.citedreference | K. Kuchitsu and L. S. Bartell, J. Chem. Phys. 36, 2460 (1962). | en_US |
dc.identifier.citedreference | K. Kuchitsu and L. S. Bartell, J. Chem. Phys. 36, 2470 (1962). | en_US |
dc.identifier.citedreference | L. S. Bartell, K. Kuchitsu, and R. J. deNeui, J. Chem. Phys. 35, 1211 (1961). | en_US |
dc.identifier.citedreference | Y. Murata, T. Fukuyama, and M. Tanimoto, “Unit for the Precise Measurement of Electron‐Diffraction Intensities by Gas Molecules. II,” Bull. Chem. Soc. Japan (to be published). | en_US |
dc.identifier.citedreference | Y. Morino and T. Iijima, Bull. Chem. Soc. Japan 35, 1661 (1962). | en_US |
dc.identifier.citedreference | K. Kuchitsu and S. Konaka, J. Chem. Phys. 45, 4342 (1966). Note that in Eq. (9) of this reference the coefficient of Σ0′(ζsσgσ′(α))2Σ0′(ζsσgσ′(α))2 should read −3−3 instead of +1.+1. | en_US |
dc.identifier.citedreference | K. Kuchitsu, J. P. Guillory, and L. S. Bartell, J. Chem. Phys. 49, 2488 (1968). | en_US |
dc.identifier.citedreference | K. Kuchitsu, J. Chem. Phys. 44, 906 (1966). | en_US |
dc.identifier.citedreference | Y. Morino, K. Kuchitsu, Y. Hori, and M. Tanimoto, Bull. Chem. Soc. Japan 41, 2349 (1968). | en_US |
dc.identifier.citedreference | K. Kuchitsu, T. Fukuyama, and Y. Morino, J. Mol. Struct. 1, 463 (1968). | en_US |
dc.identifier.citedreference | K. Kivelson, E. B. Wilson, Jr., and D. R. Lide, Jr., J. Chem. Phys. 32, 205 (1960). | en_US |
dc.identifier.citedreference | W. J. Lafferty, D. R. Lide, and R. A. Toth, J. Chem. Phys. 43, 2063 (1965). | en_US |
dc.identifier.citedreference | L. S. Bartell and H. K. Higginbotham, J. Chem. Phys. 42, 851 (1965). | en_US |
dc.identifier.citedreference | D. W. Lepard, D. M. C. Sweeny, and H. L. Welsh, Can. J. Phys. 40, 1567 (1962). | en_US |
dc.identifier.citedreference | D. W. Lepard, D. E. Shaw, and H. L. Welsh, Can. J. Phys 44, 2353 (1966). | en_US |
dc.identifier.citedreference | H. C. Allen, Jr. and E. K. Plyler, J. Chem. Phys. 31, 1062 (1959). | en_US |
dc.identifier.citedreference | W. J. Lafferty and E. K. Plyler, J. Chem. Phys. 37, 2688 (1962). | en_US |
dc.identifier.citedreference | A. R. H. Cole, W. J. Lafferty, and R. J. Thibault, “Rotational Fine Structure of the Perpendicular Band, ν7,ν7, of Ethane,” J. Mol. Spectry. (to be published). | en_US |
dc.identifier.citedreference | I. Nakagawa (private communication). | en_US |
dc.identifier.citedreference | G. E. Hansen and D. M. Dennison, J. Chem. Phys. 20, 313 (1952). | en_US |
dc.identifier.citedreference | M. Iwasaki and K. Hedberg, J. Chem. Phys. 36, 2961 (1962). | en_US |
dc.identifier.citedreference | T. Oka and Y. Morino, J. Mol. Spectry. 6, 472 (1961). | en_US |
dc.identifier.citedreference | D. E. Shaw, D. W. Lepard, and H. L. Welsh, J. Chem. Phys. 42, 3736 (1965). | en_US |
dc.identifier.citedreference | From this relation, a similar rz(C‐H)−rz(C‐D)rz(C‐H)−rz(C‐D) may be expected for ethylene. Hence, the assumption made in Ref. 11 for the difference, 0.0040Å,0.0040Å, transferred from triatomic molecules and tetratomic molecules, may have been an overestimate. An alternative assumption, 0.002 Å, will shift the spectroscopic r∣r∣ structures of ethylene (rcc,rcc, rCH,rCH, and αCCHαCCH listed in Table VII of Ref. 11) by +0.0020Å,+0.0020Å, −0.0026Å,−0.0026Å, and +10′,+10′, respectively, and accordingly, the most probable rzrz structure will be: r(C‐H) = 1.089±0.003Å,r(C‐H)=1.089±0.003Å, r(C‐C) = 1.336±0.003Å,r(C‐C)=1.336±0.003Å, and ∠C‐C‐H = 121.9°±0.4°.∠C‐C‐H=121.9°±0.4°. | en_US |
dc.identifier.citedreference | The rotational constants A0A0 for C2H6C2H6 reported earlier (a) 2.589 cm−12.589cm−1 [L. G. Smith, J. Chem. Phys. 17, 139 (1949) ]and (b) 2.578 cm−12.578cm−1 [J. Ramanko, T. Feldman, and H. L. Welsh, Can. J. Phys. 33, 588 (1955)] lead to Ia(z)Ia(z) of 6.484 and 6.511 amu⋅Å2,6.511amu⋅Å2, respectively. Since they appear to deviate significantly from the present estimate from electron diffraction, 6.305±0.025 amu⋅Å2,6.305±0.025amu⋅Å2, the A0A0 constant revised by Lepard et al.,18 (2.671±0.005 cm−1,2.671±0.005cm−1, Ia(z) = 6.286±0.012 amu⋅Å2Ia(z)=6.286±0.012amu⋅Å2) seems to be more reasonable. | en_US |
dc.identifier.citedreference | L. S. Bartell, J. Chem. Phys. 36, 3495 (1962). | en_US |
dc.identifier.citedreference | R. C. Lord and E. Nielsen, J. Chem. Phys. 19, 1 (1951). T. Ogawa and T. Miyazawa, Spectrochim. Acta 20, 557 (1964). | en_US |
dc.identifier.citedreference | The author is grateful to I. Nakagawa for providing his unpublished calculations on the normal‐coordinate analysis of diborane and for his helpful discussions. | en_US |
dc.identifier.citedreference | L. S. Bartell and B. L. Carroll, J. Chem. Phys. 42, 1135 (1965). For structure of diborane, see Fig. 4 of this reference. | en_US |
dc.identifier.citedreference | L. S. Bartell, J. Chem. Phys. 42, 1681 (1965). | en_US |
dc.identifier.citedreference | W. J. Lafferty (private communication, December 1967), to which the author is indebted. T. Coyle, W. J. Lafferty, and A. G. Maki, J. Mol. Spectry. (to be published). | en_US |
dc.identifier.citedreference | Y. Morino, J. Nakamura, and P. W. Moore, J. Chem. Phys. 36, 1050 (1962). | en_US |
dc.identifier.citedreference | Y. Morino, S. J. Cyvin, K. Kuchitsu, and T. Iijima, J. Chem. Phys. 36, 1109 (1962). | en_US |
dc.identifier.citedreference | K. Kuchitsu and Y. Morino, Bull. Chem. Soc. Japan 38, 805 (1965). | en_US |
dc.owningcollname | Physics, Department of |
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