Nonuniform Continuum Model for Solvatochromism Based on Frozen-Density Embedding Theory

Frozen‐density embedding theory (FDET) provides the formal framework for multilevel numerical simulations, such that a selected subsystem is described at the quantum mechanical level, whereas its environment is described by means of the electron density (frozen density; ${\rho _{\rm{B}} (\vec r)}$)....

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Bibliographic Details
Published in:	Chemphyschem Vol. 15; no. 15; pp. 3291 - 3300
Main Authors:	Shedge, Sapana Vitthal, Wesolowski, Tomasz A.
Format:	Journal Article
Language:	English
Published:	Weinheim WILEY-VCH Verlag 20-10-2014 WILEY‐VCH Verlag Wiley Wiley Subscription Services, Inc
Subjects:	Chemistry density functional calculations Exact sciences and technology General and physical chemistry molecular dynamics molecular modeling Solutions solvatochromism Theory UV/Vis spectroscopy UVNis spectroscopy density functional calculations Theory molecular modeling Molecular dynamics Density functional method Solvatochromism Models Density Modeling molecular dynamics UV/Vis spectroscopy solvatochromism
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Summary:	Frozen‐density embedding theory (FDET) provides the formal framework for multilevel numerical simulations, such that a selected subsystem is described at the quantum mechanical level, whereas its environment is described by means of the electron density (frozen density; ${\rho _{\rm{B}} (\vec r)}$). The frozen density ${\rho _{\rm{B}} (\vec r)}$ is usually obtained from some lower‐level quantum mechanical methods applied to the environment, but FDET is not limited to such choices for ${\rho _{\rm{B}} (\vec r)}$. The present work concerns the application of FDET, in which ${\rho _{\rm{B}} (\vec r)}$ is the statistically averaged electron density of the solvent ${\left\langle {\rho _{\rm{B}} (\vec r)} \right\rangle }$. The specific solute–solvent interactions are represented in a statistical manner in ${\left\langle {\rho _{\rm{B}} (\vec r)} \right\rangle }$. A full self‐consistent treatment of solvated chromophore, thus involves a single geometry of the chromophore in a given state and the corresponding ${\left\langle {\rho _{\rm{B}} (\vec r)} \right\rangle }$. We show that the coupling between the two descriptors might be made in an approximate manner that is applicable for both absorption and emission. The proposed protocol leads to accurate (error in the range of 0.05 eV) descriptions of the solvatochromic shifts in both absorption and emission. Simplifying solvents: Frozen‐density embedding theory (FDET) has been developed to include a statistically averaged electron density of the solvent. The model has been used to investigate specific solute–solvent interactions and to accurately describe solvatochromic shifts in both absorption and emission.
Bibliography:	istex:FCE40F8F1EBCC6459D6955AF72CCC9337B16A9CE ArticleID:CPHC201402351 ark:/67375/WNG-25NPQX48-D Swiss National Science Foundation - No. 200021_152775 COST (European Cooperation in Science and Technology) Action - No. CM1002 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	1439-4235 1439-7641
DOI:	10.1002/cphc.201402351