Solvent dielectric attenuation of substituent effects. Field transmission dependence on cavity boundary representation

Journal Article · Wed Sep 08 04:00:00 EDT 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00382a010· OSTI ID:6539332

Ehrenson, S

Previously developed methods for introducing radial dependence to the bulk dielectric of continuum solvents in order to take into account electrostatic field effects at and near the cavity boundary have been applied to the Kirkwood-Westheimer (KW) substituent-reactivity theory. Functions assumed to model electrical saturation and electrostriction are shown capable of causing from 10% to fourfold variations in typical solvent effects on pole-pole and pole-dipole interactions within spherical cavities. The relative effects on the latter are significantly larger; their introduction generally improves the agreement of theory with reactivity observables. Various intrinsic details of the original and modified theories are examined by means of generalized geometry dependencies for epsilon/sub eff/ and the possible interrelation of site location and dielectric modification effects scrutinized. Extensions to cavities of other shapes and to anisotropies for the bulk dielectric are also briefly outlined. 7 figures, 1 table.

• Research Organization: Brookhaven National Lab., Upton, NY
• OSTI ID: 6539332
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:18; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ATTENUATION
DIELECTRIC PROPERTIES
ELECTRICAL PROPERTIES
MATHEMATICAL MODELS
PERMITTIVITY
PHYSICAL PROPERTIES
POLAR COMPOUNDS
SOLVENTS