A Statistical Model of Steady-state Solvatochromism

This work provides a description of the solvatochromic effect in terms of a hard-sphere model taking into account the microscopic parameters of the solution. The average energies of the solute-solvent system were calculated for Franck-Condon and relaxed states assuming pairwise electrostatic interactions between polarizable, dipolar molecules contained in clusters made of 1-solute and 10-solvent molecules. This in turn allowed us to estimate the values of the solvatochromic shifts. The dependence of these shifts on temperature and electronic properties of molecules expressed in terms of their polarity and polarizability was investigated.