Showing papers by "Henry Eyring published in 1964"

Significant Structure Theory of Surface Tension

Abstract: The approximation is made that the dividing surface between a liquid and its vapor phase is a monomolecular layer, in which a molecule has a free volume larger than for an interior molecule and a potential energy less than for the latter. By introducing the approximation into the significant structure theory of liquids, a partition function fN is derived which involves the terms belonging to the surface as well as to the bulk liquid. The surface tension is calculated by γ = (∂A/∂Ω)N,V,T, where A is the Helmholtz free energy which equals —kTlnfN, Ω is the surface area, N the total number of molecules in the system, V the volume of the liquid, and T the absolute temperature. The surface tensions of nonpolar substances at various temperatures are calculated with good results. Our theory is compared with other theories, and it is found that the present theory most satisfactorily predicts the surface tensions at various temperatures.

Variational Calculation of the Optical Activity of 3‐Methylcyclopentanone (One‐Electron Theory)

Abstract: The variational principle is applied to the one‐electron theory of optical rotation of 3‐methylcyclopentanone. The numerical results are compared with the results obtained by Kauzmann, Walter, and Eyring. The variational method is better than the perturbation theory for the visible, where many excited states make appreciable contributions, since suitable eigenfunctions for excited states are hard to come by. The procedures employed should be widely applicable.

Correlation between the significant liquid structure theory and the cell theory.

Abstract: 9 Albert, A., Biochem. J., 50, 690 (1952). 10 Akedo, H., and H. N. Christensen, J. Biol. Chem., 237, 118 (1962). Frimpter, G. W., J. Biol. Chem., 236, PC51 (1961). laDent, C. E., and G. A. Rose, Quart. J. Med., 20, 205 (1951). 3Webber, W. A., Am. J. Physiol., 202, 577 (1962). 14 Winter, C. G., and H. N. Christensen, J. Biol. Chem., in press. 1Christensen, H. N., H. Akedo, D. L. Oxender, and C. G. Winter, in Amino Acid Pools, ed. J. T. Holden (Amsterdam: Elsevier, 1962). 16 Christensen, H. N., Biological Transport (New York: W. A. Benjamin, Inc., 1962), pp. 61-65.

Mobile Bond Orders of Some Polyphenyls from SCF—LCAO—MO Theory

Abstract: For the present calculation of the mobile bond orders of para‐quaterphenyl and meta‐terphenyl molecules, Pople's simplified SCF—LCAO—MO theory for unsaturated hydrocarbon molecules in their ground states is utilized. The symmetry orbitals for these molecules are formulated in order to simplify the calculations by the use of group theory. The symmetry properties of these molecules and the pairing properties of the molecular orbitals are discussed. Planar configurations of both molecules are assumed as a first approximation. The unreasonable mobile bond orders calculated from the Huckel MO theory are improved in the present calculations. The results are discussed in connection with the recent experimental values of the bond lengths of biphenyl.