Two-response-time model based on CM2/INDO/S2 electrostatic potentials for the dielectric polarization component of solvatochromic shifts on vertical excitation energies

A model is presented for the electrostatic component of solvatochromic shifts on vertical electronic excitation energies. The model, called vertical electrostatic model 42 (VEM42), is based on representing the solute by a set of distributed atomic monopoles obtained by charge model 2 (CM2) and representing the solvent by its static and optical dielectric constants. The theory is applied here with intermediate neglect of differential overlap for spectroscopy-parameterization 2 (INDO/S2) configuration interaction wave functions. The model is implemented in the ZINDO electronic structure code package. We present illustrative applications to the singlet n! excitation of acetone in nine solvents. When the electrostatics are augmented by one-parameter estimates of dispersion and hydrogen-bonding contributions, the experimental solvatochromic shifts in the nine solvents are reproduced with a mean unsigned error of 65 cm 1 (0.2 kcal/mol). These calculations present a compelling picture of the quantitative origin of the solvatochromic red and blue shifts in this prototype n! excitation.

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