By I. Prigogine, Stuart A. Rice
The Advances in Chemical Physics sequence offers the chemical physics and actual chemistry fields with a discussion board for severe, authoritative reviews of advances in each quarter of the self-discipline. jam-packed with state-of-the-art study mentioned in a cohesive demeanour no longer stumbled on somewhere else within the literature, each one quantity of the Advances in Chemical Physics sequence serves because the excellent complement to any complicated graduate category dedicated to the research of chemical physics
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Extra resources for Advances in Chemical Physics, Volume 9
The growing hard sphere which produces the spherical cavity of the preceding sections is a special case of such particle scaling. /4 (82) where E measures the depth of the potential well and a is a distance parameter usually proportional to the value of r at the position of the potential minimum (see Fig. 2). Frequently we choose for a the value of r a t this minimum. Another choice, and one which we shall adopt in view of our interest in the hard core, is the value of r at the point where u(r) is 0 as it rises steeply to assure repulsion.
83)) 0 reduces to G. a, so that the integrand in Eq. (54) may be moved in front of the integral sign with only g(Aa) appearing. I n the parlance of the preceding sections this is G(Aa). Helfand et have established the counterparts in the present formalism of Eqs. (34), (30), (52), (14), (40), (48),(38), and (50). 32 HOWARD REISS We list all but the last two of these, employing a notation suitable for the 8 formalism: p/kT 7 1 +- ;~a'pp"O(1 , p ) (85) i. '~0(1', p)dA' (W In Eq. ('86) p A is the concentration of 1,-cules and A: is given by Eq.
To remove the solute effectively from the fluid it is necessary t o permit the point molecule to penetrate to the centers of the surrounding solvent -a/2, and Y = 0. Thus, molecules. [Jnder this circumstance b all the configurations accessible to the solvent molecules before the introduction of the solute are once again accessible, and the solute will have been in effect removed. When we look upon the cavity as having been produced by a solute, the point 7 = a/2 is unique. It corresponds to a point solute and any further reduction in the size of the corresponding cavity requires us to redefine the intermolecular potential.