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Surface local ionization energies and electrostatic potentials of the conjugate bases of a series of cyclic hydrocarbons in relation to their aqueous acidities
Author(s) -
Murray Jane S.,
Brinck Tore,
Politzer Peter
Publication year - 1991
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560400713
Subject(s) - chemistry , ionization , conjugate , ab initio , aqueous solution , ionization energy , cubane , maxima and minima , computational chemistry , potential energy surface , series (stratigraphy) , molecule , ion , organic chemistry , biology , mathematical analysis , paleontology , mathematics
Abstract We have computed surface local ionization energies [Ī S ( r )] and electrostatic potential minima ( V min ) for the conjugate bases of a series of cyclic hydrocarbons, using an ab initio self‐consistent field–molecular orbital approach. Our Ī S ( r ) and V min results are discussed in relation to the acidities of the parent hydrocarbons. A good correlation exists between experimentally determined p K a values and the lowest surface Ī( r ) values [Ī S , min ], providing a predictive capability for estimating unknown p K a 's. The electrostatic potential minima, V min , do not relate as well to p K a as does Ī S , min . Using our Ī S , min versus p K a correlation, we predict the p K a 's of the strained cage polyhedranes cubane, triprismane, and tetrahedrane to be 36, 32, and 26, respectively.