ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
We have computed surface local ionization energies [ĪS(r)] and electrostatic potential minima (Vmin) for the conjugate bases of a series of cyclic hydrocarbons, using an ab initio self-consistent field-molecular orbital approach. Our ĪS(r) and Vmin results are discussed in relation to the acidities of the parent hydrocarbons. A good correlation exists between experimentally determined pKa values and the lowest surface Ī(r) values [ĪS,min], providing a predictive capability for estimating unknown pKa's. The electrostatic potential minima, Vmin, do not relate as well to pKa as does ĪS,min. Using our ĪS,min versus pKa correlation, we predict the pKa's of the strained cage polyhedranes cubane, triprismane, and tetrahedrane to be 36, 32, and 26, respectively.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560400713
