Vibration‐Hindered Rotation Interactions in Methyl Alcohol. The J=0→1 Transition
dc.contributor.author | Hecht, Karl T. | en_US |
dc.contributor.author | Dennison, David M. | en_US |
dc.date.accessioned | 2010-05-06T21:26:06Z | |
dc.date.available | 2010-05-06T21:26:06Z | |
dc.date.issued | 1957-01 | en_US |
dc.identifier.citation | Hecht, Karl T.; Dennison, David M. (1957). "Vibration‐Hindered Rotation Interactions in Methyl Alcohol. The J=0→1 Transition." The Journal of Chemical Physics 26(1): 48-69. <http://hdl.handle.net/2027.42/69972> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/69972 | |
dc.description.abstract | The hindered rotation fine structure of the J=0→1, K=0→0 transition which has been observed by Venkateswarlu, Edwards, and Gordy in normal methanol as well as in five additional isotopic species can be understood only qualitatively on the basis of earlier investigations of the theory of hindered rotation in methanol. It has been shown that the frequency separations between the various torsional transitions and the splitting of each of these can be explained quantitatively by including in the theory the effects of the vibration‐hindered rotation interactions during the rotation of the whole molecular framework in space. The effects of the asymmetry of the rigid hindered rotator, the Coriolis interactions, and the centrifugal distortion of the molecule are discussed separately. A frequency formula for the transition is derived which contains essentially only four new rotational constants. Three of these depend solely upon the known structure of the molecule and the elastic force constants and can therefore be calculated from a knowledge of the vibrational spectrum. Since this latter has never been analyzed in more than a rough way some small adjustments have been made in the indicated values of the elastic constants which are within the limits of uncertainty. This adjustment is made for the normal molecule after which the three rotational constants are calculated for the remaining isotopic species without further adjustment. The fourth constant in the frequency formula describes the dependence of the barrier height upon the normal coordinates and is the only constant which must be determined empirically for each isotopic species. It has thus been possible to predict the 30 observed separations and splittings with the aid of essentially only six empirical constants. The agreement with experiment is remarkably good with one possible exception where the theory predicts for the fully deuterated methanol a very large splitting of the normal state line whereas the line in question is observed to be single. It is not improbable, however, that the large splitting actually exists and that the second component lay too far away to be recognized. | en_US |
dc.format.extent | 3102 bytes | |
dc.format.extent | 1552519 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 | Vibration‐Hindered Rotation Interactions in Methyl Alcohol. The J=0→1 Transition | 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 | Harrison M. Randall Laboratory of Physics, The University of Michigan, Ann Arbor, Michigan | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/69972/2/JCPSA6-26-1-48-1.pdf | |
dc.identifier.doi | 10.1063/1.1743263 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
dc.identifier.citedreference | Venkateswarlu, Edwards, and Gordy, J. Chem. Phys. 23, 1195 (1955). | en_US |
dc.identifier.citedreference | J. S. Koehler and D. M. Dennison, Phys. Rev. 57, 1006 (1940). | en_US |
dc.identifier.citedreference | D. G. Burkhard and D. M. Dennison, Phys. Rev. 84, 408 (1951). | en_US |
dc.identifier.citedreference | E. V. Ivash and D. M. Dennison, J. Chem. Phys. 21, 1804 (1953). | en_US |
dc.identifier.citedreference | D. Kivelson, J. Chem. Phys. 22, 1733 (1954); 23, 2230 and 2236 (1955). | en_US |
dc.identifier.citedreference | This process is illustrated in detail in the preceding paper for the hindered rotation—over‐all space rotation interactions in the case of the simple theory of hindered rotation. | en_US |
dc.identifier.citedreference | The matrix elements of the Hamiltonian are given by Eqs. (12). | en_US |
dc.identifier.citedreference | P. Venkateswarlu and W. Gordy, J. Chem. Phys. 23, 1200 (1955). | en_US |
dc.identifier.citedreference | Since the theory of the vibration‐hindered rotation interactions in methyl alcohol is examined in detail in this paper it would have been possible to compute new effective bond distances and angles for which the averaging effects of the vibrationhyphen;hindered rotation interactions (but not the ordinary vibrationhyphen;rotation interactions) have been taken into account. It is certain that these would introduce only very minor changes. | en_US |
dc.identifier.citedreference | Ivash, Li, and Pitzer, J. Chem. Phys. 23, 1814 (1955). References to earlier work are given in this paper. | en_US |
dc.identifier.citedreference | See reference 3; also, D. G. Burkhard, “Coupling of the hindered rotation and the OH rocking motion in methyl alcohol” (private communiation). | en_US |
dc.identifier.citedreference | See Eq. (9) of the preceding paper. | en_US |
dc.identifier.citedreference | See, e.g., H. H. Nielsen, Revs. Modern Phys. 23, 90 (1951); or E. B. Wilson and J. B. Howard, J. Chem. Phys. 4, 260 (1936). | en_US |
dc.identifier.citedreference | In the O‐H rocking model the constant CυCυ was determined largely by a perturbation term of the form 1/2(P+′Pz′+Pz′P+′)μ13(δα).1∕2(P+′Pz′+Pz′P+′)μ13(δα). Now there are additional perturbation terms in the Hamiltonian of the form P−′pα′(δqj)2ζαjj,P−′pα′(δqj)2ζαjj, for example, which give important contributions to this constant. | en_US |
dc.identifier.citedreference | As listed by Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (D. Van Nostrand Company, Inc., New York, 1945), p. 170. | en_US |
dc.identifier.citedreference | A large n = 0→0n=0→0 splitting for this isotopic molecule has also been predicted on the basis of the rigid model hindered rotator by J. D. Swalen by a different method [J. Chem. Phys. 23, 1739 (1955)]. | en_US |
dc.identifier.citedreference | N. W. McLachlan, Theory and Application of Mathieu Functions (The Clarendon Press, Oxford, England, 1946), p. 19. | en_US |
dc.owningcollname | Physics, Department of |
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