Equation Tolman parameter

Ve see in Figure 7 that Tolman s representation of the radially dependent surface tension also leads to a vanishing thermodynamic barrier, at high but metastable supersaturations, when a value of 6 computed from solutions of the YBG equation on the planar interface is used. This value of the Tolman parameter is consistent with values obtained from simulation studies of the planar Lennard-Jones surface (28,29). It is apparent that the physical picture of nucleation is highly dependent upon the assumed radial dependence of the surface tension. 

The surface tension is very insensitive to changes in supersaturation. While the planar surface tension is, of course, temperature-dependent, the ratio of the small system surface tension to the planar limit is nearly independent of temperature. This simplicity in the functional dependence of the radially dependent surface tension has been anticipated by a number of workers in terms of the parameter defined by Equation 18. Tolman obtained the following differential equation... 

While many workers have used Tolman s steric parameter (the cone angle), not nearly as many have used his electronic parameter. The latter represents the net total of all electronic effects as reflected in the value of the vfCO) vibration (i.e. the contributions of a and n bonding are unresolved) of the LNi(CO)3 (L = phosphine) complex. Tolman further analyzed the contributions of various substituents to v by equation (55). 

Having obtained values of the descriptors for each of the potentially relevant properties, one then consUucts an equation in which the reaction energy or barrier height is expressed as a linear combination of the descriptors. Thus, in the alkyl bromide BDE example, one might develop an equation BDE=cone angle (0) are the properties of the alkyl radical. The empirical parameters (a, b, c, and d in this case) are then... 

---