Rotation of aromatic solutes in supercritical CO2: Are rotation times anomalously slow in the near critical regime?

Journal of Physical Chemistry A

Volumn 101, Issue 33, 1997, Pages 5852-5868

  Heitz, M P ^a   Maroncelli, M ^a  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANISOTROPY; CARBON DIOXIDE; FLUORESCENCE; MOLECULAR DYNAMICS;

MOLECULAR ROTATION; SUPERCRITICAL FLUIDS;

AROMATIC COMPOUNDS;

EID: 0031211617     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp971096v     Document Type: Article

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111. Zwanzig, R.; Harrison, A. K. J. Chem. Phys. 1985, 83, 5861.
112. See Figure 9 of ref 68 and the discussion surrounding it.
113. See, for example, the recent compilation and analysis in: Williams, A. M.; Jiang, Y.; Ben-Amotz, D. Chem. Phys. 1994, 180, 119.
114. 0 ≈ 5.
115. Horng, M.-L.; Maroncelli, M. Unpublished results.
116. In the case of rotation times and spectral shifts, this relationship is indirect. The F(ρ) functions here entail intermediate connections to the solvent viscosity or refractive index, the latter which can be expressed as simple functions of solvent density.
117. eff.
118. 39 We would favor the former interpretation. In any case, the differences between the conclusions reached in ref 39 and in our analysis of the same data illustrate the difficulty of attempting to quantifying local density augmentation. A thorough understanding of the behavior in the absence of augmentation must be available either from empirical or theoretical considerations in order to accurately determine the magnitude of the deviations that provide augmentation estimates. In many cases our understanding is only partial so as to provide a wide margin of expected behaviors, which in turn lead to large uncertainties in local density estimates.
119. Heitz, M.; Maroncelli, M. Unpublished results.
120. See for example: Stanley, H. E. Introduction to Phase Transitions and Critical Phenomena; Oxford Press: New York, 1971.
121. These two methods are reviewed in the two articles by J. R. Lakowicz and I. Gryczynski and D. J. S. Birch and R. E. Imhof in the book: Topics in Fluorescence Spectroscopy, Vol. 1: Techniques; Lakowicz, J. R., Ed.; Plenum: New York, 1991.
122. Lakowicz, J. R.; Jayaweera, R.; Joshi, N.; Gryczynski, I. Anal. Biochem. 1987, 160, 471.
123. Maroncelli, M. Unpublished results.
124. Collaborative work planned with Frank Bright.
125. See, for example the lucid discussion in: Randolph, T. W.; O-Brien, J. A.; Ganapathy, S. J. Phys. Chem. 1994, 98, 4173.