Showing papers by "Henry Eyring published in 1980"

Elementary transition state theory of the Soret and Dufour effects.

Abstract: The elementary transition state approach has been used to obtain a simple model theory for the Soret effect (thermal diffusion) and the Dufour effect. The flow of heat in the Dufour effect is identified as the transport of the enthalpy change of activation as molecules diffuse. The theory as now formulated applies only to thermodynamically ideal mixtures of substances with molecules of nearly equal size. The results of the theory conform to the Onsager reciprocal relationship. When the results were fit to data on thermal diffusion for two liquid systems, a close fit was obtained and yielded reasonable values of between 2 and 3 kcal mol-1 for enthalpy changes of activation and differences between the entropy changes of activation for the two components of between 0 and 1 cal K-1 mol-1.

Wavelength regulation in rhodopsin: effects of dipoles and amino acid side chains.

Abstract: The effects of dipoles and aromatic amino acid side-chain models on the absorption and optical activity of the rhodopsin chromophore were calculated by using perturbation theory, and the results were compared with those of a Pariser-Parr-Pople calculation for the unperturbed system. The interaction was assumed to result from purely electrostatic interactions. It was concluded that the side chains of phenylalanine and tryptophan should have no important effects. However, the charge separation in tyrosine is sufficient to cause substantial electrostatic perturbation; in fact, the effect of tyrosine is large enough to approximately many of the spectral properties of rhodopsin quantitatively. This is encouraging because the use of aromatic amino acid side-chain analogs probably provides a better physical model than the use of isolated full charges, except in the case of the counterion to the protonated Schiff base.

Temperature and Pressure Dependence of Viscosity of Quantum Liquid 4He According to Significant Structure Theory

Abstract: Both solid-like and gas-like flow structures are considered in the calculation of viscosity of liquid 4He using the significant structure theory of liquids. The predominance of quantum mechanical zero-point motion over that arising from thermal excitation is taken into account for the solid-like motion of molecules. The viscosity of liquid 4He under its own vapor pressure calculated over its whole temperature range is in reasonably good agreement with experimental data. The pressure dependence of viscosity also was obtained. The calculation does not yield good results at high densities where the free jumping of molecules into the nearest neighboring vacancies through the kinetic zero-point motion is no longer plausible.

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form

Abstract: The rotational strengths of the four longer wavelength transitions, B2u, B1u, and the two E1u, of adenosine derivatives constrained in the syn form have been investigated theoretically and experimentally. The theory combines a complete neglect of differential overlap version S (CNDO/S) description of the base with a generalized bond exciton method by means of a matrix method. Rotational strength wheels for these transitions showing the rotational strength as a function of the glycosidic rotational angles are presented and sector rules discussed. Similar sector rules are predicted for purine nucleoside derivatives containing the 6-amino substituent, regardless of heteroatom content at positions 1 or 3 of the base. The sector rules for the B2u rotational strength of purine nucleosides lacking the 6-amino substituent are strongly influenced by aza substitution. The circular dichroism spectra of 3-deazaadenosine, 8-(α-hydroxyisopropyl)-adenosine, and other purine nucleosides having a strong preference for the syn conformation are presented and compared with the theoretical results.

Application of the Eyring-Stover survival theory to soil-related functions.

Abstract: The fit of the Eyring-Stover statistical survival theory was found to be precise when applied to diverse soil-related functions.

Significant structure theory applied to liquid 4He

Abstract: The large kinetic zero-point motion of 4He molecules has been properly taken into account in the significant structure theory of liquids in order to describe the liquidity of liquid 4He. The Debye and the Bose-Einstein partition functions are used for the solid-like molecules of the normal fluid component and for the whole gas-like molecules, respectively. The solid-like molecules of the superfluid component are considered as ground state molecules without having positional degeneracies. The Bragg-Williams approximation of an order/disorder phase transition has been applied to the λ transition of liquid 4He. Thermodynamic and surface properties of liquid 4He have been calculated up to the critical point. The results are satisfactory when compared with the observed values.