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Solvatochromism of the π* ← n transition of acetone by combined quantum mechanical—classical mechanical calculations
Author(s) -
De Vries Alex H.,
Van Duijnen Piet Th.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)57:6<1067::aid-qua5>3.0.co;2-r
Subject(s) - solvatochromism , solvent effects , solvation , solvent models , chemistry , polarizability , solvent , acetonitrile , dielectric , london dispersion force , excited state , computational chemistry , dispersion (optics) , polarizable continuum model , acetone , molecule , organic chemistry , physics , quantum mechanics , van der waals force
The solvent shift of the π* ← n transition of acetone in water, acetonitrile, and tetrachloromethane was calculated in a combined quantum mechanical—classical mechanical approach, using both dielectric continuum and explicit, polarizable molecular solvent models. The explicit modeling of solvent polarizability allows for a separate analysis of electrostatic, induction, and dispersion contributions to the shifts. The calculations confirm the qualitative theories about the mechanisms behind the blue shift in polar solvents and the red shift in nonpolar solvents, the solvation of the ground state due to electrostatic interactions being preferential in the former, and favorable dispersion interaction with the excited state, in the latter case. Good quantitative agreement for the solvent shift between experiment (+1,700, +400, and −350 cm −1 in water, acetonitrile, and tetrachloromethane, respectively) and the explicit solvent model (+1,821, +922, and −381 cm −1 ) was reached through a modest Monte Carlo sampling of the solvent degrees of freedom. A consistent treatment of the solvent could only be realized in the molecular solvent model. The dielectric‐only model needs reparameterization for each solvent. © 1996 John Wiley & Sons, Inc.