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Volumn 102, Issue 14, 1998, Pages 2437-2453

The effect of solvent density inhomogeneities on solute dynamics in supercritical fluids: A theoretical perspective

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Indexed keywords


EID: 0000774575     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp972382+     Document Type: Review
Times cited : (148)

References (174)
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    • 11644280453 scopus 로고    scopus 로고
    • note
    • Some authors reserve the name SCF for fluids having a pressure greater than the critical pressure in addition to having a temperature above the critical temperature.
  • 29
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    • note
    • The scaling axis is the analytic continuation of the gas-liquid coexistence curve into the supercritical regime.
  • 32
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    • note
    • The reader should be aware that most works published prior to about 1990 invoke this misleading interpretation.
  • 73
    • 11644292730 scopus 로고    scopus 로고
    • note
    • The range of solvent density enhancements is only controlled by the indirect effects when the correlation length ξ exceeds the range of the solute-solvent intermolecular potential.
  • 103
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    • note
    • 28
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    • note
    • Rigorously, the exponential asymptotic form of g(r) arises from a Taylor Series expansion in the long wavelength limit, see ref 28.
  • 106
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    • note
    • The expansion is actually conducted on the Fourier transform of the direct correlation function; see ref 28.
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    • note
    • 12 is required to remain finite only in the classical Ornstein-Zernike theory. See ref 28 for a detailed discussion of this point.
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    • note
    • 2, depends only on the direct density enhancements. While this definition of the solvation energy differs from that considered by Chialvo and Cummings, who use the ideal solution (pure solvent) as the reference state, both expressions lead to the same conclusion regarding the dependence on only the "local" density enhancements.
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    • note
    • No general guidelines for determining how close is too close exist. To date, simulations have been confirmed, with more or less rigor, on a case by case basis.
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    • de Pablo, J. J.; Prausnitz, J. M.; Strauch, H. J.; Cummings, P. T. J. Chem. Phys. 1990, 93, 7355. Strauch, J. P.; Cummings, P. T. J. Chem. Phys. 1992, 96, 864.
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    • note
    • 2, where quadrupolar interactions can be important.
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    • Berne, B. J. In Multiple Time Scales; Brackbill, J. U., Cohen, B. I., Eds.; Academic Press: New York, 1985.
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    • note
    • R) with ΔG = ΔU - TΔS, where ΔS is the change in the entropic contributions of the solute intramolecular and rotational motions between the transition state and reactant complexes.
  • 158
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    • note
    • Equation 17 in mole fraction (χ) units is equivalent to eq 7 of ref 1 if the standard states are taken to be the pure components (χ = 1). Additionally, if concentration units are used, eq 17 gives eq 2 of ref 1.
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    • note
    • The density distribution for this system using a spatial (as opposed to an atom-centered) function has been examined previously (ref 168) in the context of a length-scaling method for determining the critical exponent for the correlation length.
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    • note
    • A very similar time correlation function has been examined by O'Brien, et al. (ref 89) for a three-dimensional LJ SCF solution. Although their results suggest that the time scale of local solvent fluctuations can be quite different for solute and solvent, the poor quality of their data makes their results inconclusive.
  • 174
    • 11644304696 scopus 로고    scopus 로고
    • note
    • 110


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