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

Zhou, Xiuwen, Kaminski, Jakub W. and Wesolowski, Tomasz A. (2011) Multi-scale modelling of solvatochromic shifts from frozen-density embedding theory with non-uniform continuum model of the solvent: the coumarin 153 case. Physical Chemistry Chemical Physics, 13 22: 10565-10576. doi:10.1039/c0cp02874f


Author Zhou, Xiuwen
Kaminski, Jakub W.
Wesolowski, Tomasz A.
Title Multi-scale modelling of solvatochromic shifts from frozen-density embedding theory with non-uniform continuum model of the solvent: the coumarin 153 case
Journal name Physical Chemistry Chemical Physics   Check publisher's open access policy
ISSN 1463-9076
1463-9084
Publication date 2011-06-14
Sub-type Article (original research)
DOI 10.1039/c0cp02874f
Open Access Status Not yet assessed
Volume 13
Issue 22
Start page 10565
End page 10576
Total pages 12
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted 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 solvent 〈ρB(r)〉 is used as the frozen density. 〈ρB(r)〉 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.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Mathematics and Physics
 
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