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An interacting segment model of molecular electric tensor properties: Theory and application to electric dipole moments of the halogenated methanes

dc.contributor.authorMiller, C. K.en_US
dc.contributor.authorOrr, B. J.en_US
dc.contributor.authorWard, J. F.en_US
dc.date.accessioned2010-05-06T20:44:05Z
dc.date.available2010-05-06T20:44:05Z
dc.date.issued1977-09-01en_US
dc.identifier.citationMiller, C. K.; Orr, B. J.; Ward, J. F. (1977). "An interacting segment model of molecular electric tensor properties: Theory and application to electric dipole moments of the halogenated methanes." The Journal of Chemical Physics 67(5): 2109-2118. <http://hdl.handle.net/2027.42/69524>en_US
dc.identifier.urihttps://hdl.handle.net/2027.42/69524
dc.description.abstractA model is developed to describe trends in molecular properties such as electric dipole moment, polarizabilities, and hyperpolarizabilities for series of structurally related molecules. The model takes account of intramolecular electrostatic interactions, which give rise to induced electric moments in the various segments of the molecule. For this purpose each molecular segment is ascribed a set of ’’bare’’ electric tensor properties, which describe the hypothetical situation where intersegment interactions are absent, and a corresponding set of ’’dressed’’ properties, which include the effects of the intramolecular field. Any overall molecular electric tensor property is then obtained by summing the appropriate dressed segment properties. After theoretical development the model is used to fit electric dipole moment data for the 12 halogenated methanes CXnY4−n(X,Y=H,F,Cl;n=0–4), for which a simple bond additivity model is known to be inadequate and which severely test any theory of induced dipole moments. The results of such an analysis are highly satisfactory and indicate that the model should also give an adequate description of higher‐order electric tensor properties.en_US
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dc.publisherThe American Institute of Physicsen_US
dc.rights© The American Institute of Physicsen_US
dc.titleAn interacting segment model of molecular electric tensor properties: Theory and application to electric dipole moments of the halogenated methanesen_US
dc.typeArticleen_US
dc.subject.hlbsecondlevelPhysicsen_US
dc.subject.hlbtoplevelScienceen_US
dc.description.peerreviewedPeer Revieweden_US
dc.contributor.affiliationumRandall Laboratory of Physics, The University of Michigan, Ann Arbor, Michigan 48109en_US
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/69524/2/JCPSA6-67-5-2109-1.pdf
dc.identifier.doi10.1063/1.435097en_US
dc.identifier.sourceThe Journal of Chemical Physicsen_US
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dc.identifier.citedreferenceWe use conventional Cartesian tensor notation, in which Greek suffixes denote X, Y, Z components and in which summation over those components is understood when the same Greek suffix is repeated.en_US
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dc.identifier.citedreferenceWe use the shorthand notation ⟨T⋅⟩i⟨T⋅X̂⟩i to represent summations of the form Σj ≠ iTijj,Σj≠iTijX̂j, where j is a dummy suffix. The notation ⟨T⋅⟩is⟨T⋅X̂⟩is specifies a product of s such terms, each involving summation over a distinct dummy suffix.en_US
dc.identifier.citedreferenceIt should be noted that we define our interaction tensors TijTij with opposite sign to that adpoted by Applequist et al.14 Our matrix MijMij is otherwise identical to their matrix Bij.Bij.en_US
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dc.identifier.citedreferenceA recent review is given by W. B. Person and D. Steele, Molecular Spectroscopy edited by R. F. Barrow, D. A. Long, and D. J. Millen (Chemical Society, London, 1974), Vol. 2, p. 357.en_US
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dc.identifier.citedreferenceIn Refs. 1 and 2 K(0;0,ω,−ω)K(0;0,ω,−ω) is erroneously given as ⅜;38; the correct value is .32.en_US
dc.owningcollnamePhysics, Department of


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