Spectroscopic studies of p-(N,N-dimethylamino) benzonitrile and ethyl p-(N,N-dimethylamino) benzoate in supercritical trifluoromethane, carbon dioxide, and ethane
- Univ. of Texas, Austin, TX (United States)
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.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 232075
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 114; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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