Two-Response-Time Model Based on CM2/INDO/S2 Electrostatic Potentials for the Dielectric Polarization Component of Solvatochromic Shifts on Vertical Excitation Energies

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Abstract

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 → π* 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 → π* excitation.

Original languageEnglish (US)
Pages (from-to)264-280
Number of pages17
JournalInternational Journal of Quantum Chemistry
Volume77
Issue number1
DOIs
StatePublished - Mar 5 2000

Keywords

  • Blue shift
  • Configuration interaction
  • Dispersion interactions
  • Hydrogen bonding
  • Implicit solvent
  • Liquid
  • Nonequilibrium free energy
  • Polarizability
  • Reaction field
  • Red shift

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