Solvation and solvatochromism in CO2-expanded liquids. 3. The dynamics of nonspecific preferential solvation

Chet Swalina, Sergei Arzhantsev, Hongping Li, Mark Maroncelli

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Subpicosecond time-resolved fluorescence of trans-4-dimethylamino-4′- cyanostilbene (DCS) is used to measure solvation dynamics in the gas-expanded liquid (GXL) system CH3CN + CO2 at 25°C along the liquid-vapor coexistence curve. These measurements are supplemented by measurements of the steady-state solvatochromism of DCS and of its rotation and isomerization times. Molecular dynamics computer simulations and a semiempirical spectral model that reproduces the observed solvatochromism in this system are used to interpret the experimental results. Simulations indicate that at compositions of xCO2 > 0.5, the cybotactic region surrounding DCS is enriched in CH3CN molecules, and the extent of this enrichment is greater in S1 than that in S0. Solvation dynamics are dominated by the CH3CN component. These dynamics are biphasic, consisting of a subpicosecond inertial component, followed by a slower picosecond component, related to the redistribution of CH3CN molecules between the cybotactic region and the bulk solvent.

Original languageEnglish (US)
Pages (from-to)14959-14970
Number of pages12
JournalJournal of Physical Chemistry B
Volume112
Issue number47
DOIs
StatePublished - Nov 27 2008

Fingerprint

Solvation
solvation
Liquids
liquids
Molecules
Isomerization
isomerization
Molecular dynamics
molecules
computerized simulation
Gases
Fluorescence
Vapors
vapors
molecular dynamics
fluorescence
Computer simulation
curves
Chemical analysis
gases

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. 3. The dynamics of nonspecific preferential solvation",
abstract = "Subpicosecond time-resolved fluorescence of trans-4-dimethylamino-4′- cyanostilbene (DCS) is used to measure solvation dynamics in the gas-expanded liquid (GXL) system CH3CN + CO2 at 25°C along the liquid-vapor coexistence curve. These measurements are supplemented by measurements of the steady-state solvatochromism of DCS and of its rotation and isomerization times. Molecular dynamics computer simulations and a semiempirical spectral model that reproduces the observed solvatochromism in this system are used to interpret the experimental results. Simulations indicate that at compositions of xCO2 > 0.5, the cybotactic region surrounding DCS is enriched in CH3CN molecules, and the extent of this enrichment is greater in S1 than that in S0. Solvation dynamics are dominated by the CH3CN component. These dynamics are biphasic, consisting of a subpicosecond inertial component, followed by a slower picosecond component, related to the redistribution of CH3CN molecules between the cybotactic region and the bulk solvent.",
author = "Chet Swalina and Sergei Arzhantsev and Hongping Li and Mark Maroncelli",
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Solvation and solvatochromism in CO2-expanded liquids. 3. The dynamics of nonspecific preferential solvation. / Swalina, Chet; Arzhantsev, Sergei; Li, Hongping; Maroncelli, Mark.

In: Journal of Physical Chemistry B, Vol. 112, No. 47, 27.11.2008, p. 14959-14970.

Research output: Contribution to journalArticle

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AU - Arzhantsev, Sergei

AU - Li, Hongping

AU - Maroncelli, Mark

PY - 2008/11/27

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