Microsolvation effects on the pi(*) -pi electronic transitions in simple aromatic chromophores: The role of the Slater-type Gaussian orbitals in the complete active space self-consistent field approach

摘要

One of the most studied feature of aromatic molecular clusters in the gas phase is the shift of the pi(*)<-pi electronic transitions between the bare aromatic chromophore and its clusters. In the present ab initio complete active space self-consistent field study the coupling of the basis set superposition error and counterpoise procedure and a combination of Pople- and Slater-type Gaussian basis sets has been proven to reproduce quantitatively the gas-phase experimental shifts. The quantal results are here analyzed with respect to the electrostatic and polarization forces and electron density differences, and connected with the sign of the shifts of the electronic transitions. (c) 2006 American Institute of Physics.