Time dependent density functional theory study of charge-transfer and intramolecular electronic excitations in acetone–water systems

A recently introduced formulation of time dependent linear response density functional theory within the plane-wave pseudopotential framework [J. Hutter, J. Chem. Phys. 118, 3928 (2003)] is applied to the study of solvent shift and intensity enhancement effects of the 1A2 n→π* electronic transition in acetone, treating solute and solvent at the same level of theory. We propose a suitable formalism for computing transition intensities based on the modern theory of polarization, which is applicable to condensed-phase and finite systems alike. The gain in intensity brought about by thermal fluctuations is studied in molecular acetone at room temperature, and in gas-phase (CH3)2CO⋅(H2O)2 at 25 K. The latter system is characterized by the appearance of relatively intense features in the low-energy region of the spectrum, attributable to spurious solvent→solute charge-transfer excitations created by deficiencies in the DFT methodology. The n→π* transition can be partially isolated from the charge-transfer bands...

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