Issue 22, 2011

Multi-scale modelling of solvatochromic shifts from frozen-density embedding theory with non-uniform continuum model of the solvent: the coumarin 153 case

Abstract

For nine solvents of various polarity (from cyclohexane to water), the solvatochromic shifts of the lowest absorption band of coumarin 153 are evaluated using a computational method based on frozen-density embedding theory [Wesolowski and Warshel, J. Chem Phys., 1993, 97, 9050, and subsequent articles]. In the calculations, the average electron density of the solventρB([r with combining right harpoon above (vector)])〉 is used as the frozen density. 〈ρB([r with combining right harpoon above (vector)])〉 is evaluated using the statistical-mechanical approach introduced in Kaminski et al., J. Phys. Chem. A, 2010, 114, 6082. The small deviations between experimental and calculated solvatochromic shifts (the average deviation equals to about 0.02 eV), confirm the adequacy of the key approximations applied: (a) in the evaluation of the average effect of the solvent on the excitation energy, using the average density of the solvent instead of averaging the shifts over statistical ensemble and (b) using the approximant for the bi-functional of the non-electrostatic component of the orbital-free embedding potential, are adequate for chromophores which interact with the environment by non-covalent bonds. The qualitative analyses of the origin of the solvatochromic shifts are made using the graphical representation of the orbital-free embedding potential.

Graphical abstract: Multi-scale modelling of solvatochromic shifts from frozen-density embedding theory with non-uniform continuum model of the solvent: the coumarin 153 case

Article information

Article type
Paper
Submitted
14 Dec 2010
Accepted
15 Apr 2011
First published
13 May 2011

Phys. Chem. Chem. Phys., 2011,13, 10565-10576

Multi-scale modelling of solvatochromic shifts from frozen-density embedding theory with non-uniform continuum model of the solvent: the coumarin 153 case

X. Zhou, J. W. Kaminski and T. A. Wesolowski, Phys. Chem. Chem. Phys., 2011, 13, 10565 DOI: 10.1039/C0CP02874F

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