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Author Sun, Ya-Ping ♦ Fox, M. A. ♦ Johnston, K. P.
Sponsorship USDOE
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CHEMISTRY ♦ NITRILES ♦ ABSORPTION SPECTROSCOPY ♦ EMISSION SPECTROSCOPY ♦ ESTERS ♦ SUPERCRITICAL STATE ♦ DENSITY
Abstract Absorption and emission spectral maxima, bandwidths, and fractional contribution of twisted intramolecular charge transfer states to the observed emission of p-(N,N-dimethylamino) benzonitrile (DMABN) and ethyl P-(N,N-dimethylamino) benzoate (DMAAEB) in supercritical CHF{sub 3}, CO{sub 2} are presented. By examining a wide range of reduced densities from 0.05 to 2.2, the authors have discovered a characteristic density dependence in the spectral shifts in all three fluids. A model for these spectral effects is proposed, differentiating intermolecular interactions in three distinct regions; gas-phase solute-solvent clustering, clustering in the near-critical region, and {open_quotes}liquidlike{close_quotes} solvation. Even below a reduced density of 0.5, clustering of solvent about solute is already prevalent. 49 refs., 17 fig., 1 tab.
ISSN 00027863
Educational Use Research
Learning Resource Type Article
Publisher Date 1992-02-12
Publisher Place United States
Journal Journal of the American Chemical Society
Volume Number 114
Issue Number 4


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