Molecular calculations with the nonempirical ab initioMODPOT,VRDDO, and MODPOT/VRDDO procedures. XI. Theoretical study of the [C6H5OH ⃛OC6H5]− molecular complex: Ab initioMODPOT/VRDDO calculations and electrostatic molecular potential contour maps

The transport of C₆H₅O^? (or similarly charged moieties) through a lipoidal membrane may possibly be facilitated by forming complexes with the neutral compound. Thus, theoretical studies were performed on the model C₆H₅OH ?OC₆H₅]^? molecular complex to obtain some information concerning the possible molecular and electronic structure of such complexes. Ab initio MODPOT /VRDDO SCF calculations were carried out on the neutral-anion dimer C₆H₅OH ?OC₆H₅] to optimize the equilibrium geometry. Electrostatic molecular potential contour maps have been generated from the ab initio MODPOT /VRDDO results in the molecular plane and in the plane perpendicular to the molecular plane and intersecting the hydrogen bond O ?H? O. Difference maps have also been generated showing the change of potential on complex formation. There is a decrease of electrostatic interactions of the phenoxide anion upon complex formation with the neutral phenol. Counterpoise corrections for basis set size could not be made since calculation of the phenoxide anions in the basis set of the phenol plus the phenoxide anion led to an excited state for the phenoxide anion. This behavior is somewhat similar to that occurring in the stabilization method for excited states of negative ions as the size of the basis set is increased.