Solvation and solvatochromism in CO2-expanded liquids. 2. Experiment-simulation comparisons of preferential solvation in three prototypical mixtures

Hongping Li, Sergei Arzhantsev, Mark Maroncelli

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Electronic absorption and emission spectra of 10-bis(phenylethynyl) anthracene (PEA) and coumarin 153 (C153) are measured as functions of composition along the bubble-point curve at 25 °C in CO2-expanded cyclohexane (c-C6H12), acetonitrile (CH3CN), and methanol (CH3OH). The nonlinear dependence of the spectral frequencies on composition suggests substantial preferential solvation of both solutes by the liquid components of these mixtures. Estimates of enrichment factors (local mole fraction of a component divided by its bulk value) based on the assumption that spectral shifts are linearly related to local composition are quite large (∼10) in the cases of the C153/CH3CN + CO 2 and C153/CH3OH + CO2 systems at high x CO2. Computer simulations of anthracene, the chromophore of PEA, and C153 in these three CO2-expanded liquids are used to clarify the relationship between local composition and spectral shift. A semiempirical model consisting of additive electrostatic and dispersive interactions is able to capture the main features observed experimentally in all six solute/solvent combinations. The simulations show that the commonly used assumption of a linear relation between spectral shifts and local compositions grossly exaggerates the extent of preferential solvation in these mixtures. The collective nature of electrostatic solvation and the composition dependence of the solute's coordination number are shown to be responsible for the breakdown of this assumption.

Original languageEnglish (US)
Pages (from-to)3208-3221
Number of pages14
JournalJournal of Physical Chemistry B
Volume111
Issue number12
DOIs
StatePublished - Mar 29 2007

Fingerprint

Solvation
solvation
Anthracene
Liquids
liquids
anthracene
Chemical analysis
solutes
simulation
Experiments
Electrostatics
shift
electrostatics
Carbon Monoxide
Chromophores
Cyclohexane
Acetonitrile
coordination number
electronic spectra
cyclohexane

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

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title = "Solvation and solvatochromism in CO2-expanded liquids. 2. Experiment-simulation comparisons of preferential solvation in three prototypical mixtures",
abstract = "Electronic absorption and emission spectra of 10-bis(phenylethynyl) anthracene (PEA) and coumarin 153 (C153) are measured as functions of composition along the bubble-point curve at 25 °C in CO2-expanded cyclohexane (c-C6H12), acetonitrile (CH3CN), and methanol (CH3OH). The nonlinear dependence of the spectral frequencies on composition suggests substantial preferential solvation of both solutes by the liquid components of these mixtures. Estimates of enrichment factors (local mole fraction of a component divided by its bulk value) based on the assumption that spectral shifts are linearly related to local composition are quite large (∼10) in the cases of the C153/CH3CN + CO 2 and C153/CH3OH + CO2 systems at high x CO2. Computer simulations of anthracene, the chromophore of PEA, and C153 in these three CO2-expanded liquids are used to clarify the relationship between local composition and spectral shift. A semiempirical model consisting of additive electrostatic and dispersive interactions is able to capture the main features observed experimentally in all six solute/solvent combinations. The simulations show that the commonly used assumption of a linear relation between spectral shifts and local compositions grossly exaggerates the extent of preferential solvation in these mixtures. The collective nature of electrostatic solvation and the composition dependence of the solute's coordination number are shown to be responsible for the breakdown of this assumption.",
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Solvation and solvatochromism in CO2-expanded liquids. 2. Experiment-simulation comparisons of preferential solvation in three prototypical mixtures. / Li, Hongping; Arzhantsev, Sergei; Maroncelli, Mark.

In: Journal of Physical Chemistry B, Vol. 111, No. 12, 29.03.2007, p. 3208-3221.

Research output: Contribution to journalArticle

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AB - Electronic absorption and emission spectra of 10-bis(phenylethynyl) anthracene (PEA) and coumarin 153 (C153) are measured as functions of composition along the bubble-point curve at 25 °C in CO2-expanded cyclohexane (c-C6H12), acetonitrile (CH3CN), and methanol (CH3OH). The nonlinear dependence of the spectral frequencies on composition suggests substantial preferential solvation of both solutes by the liquid components of these mixtures. Estimates of enrichment factors (local mole fraction of a component divided by its bulk value) based on the assumption that spectral shifts are linearly related to local composition are quite large (∼10) in the cases of the C153/CH3CN + CO 2 and C153/CH3OH + CO2 systems at high x CO2. Computer simulations of anthracene, the chromophore of PEA, and C153 in these three CO2-expanded liquids are used to clarify the relationship between local composition and spectral shift. A semiempirical model consisting of additive electrostatic and dispersive interactions is able to capture the main features observed experimentally in all six solute/solvent combinations. The simulations show that the commonly used assumption of a linear relation between spectral shifts and local compositions grossly exaggerates the extent of preferential solvation in these mixtures. The collective nature of electrostatic solvation and the composition dependence of the solute's coordination number are shown to be responsible for the breakdown of this assumption.

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