What causes the vibrational lifetime plateau in supercritical fluids?

Journal of Chemical Physics

Volumn 110, Issue 8, 1999, Pages 3643-3646

  Goodyear, Grant ^a   Tucker, Susan C ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001067133     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.478253     Document Type: Article

References (32)

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25. LJ = 250 timesteps, corresponding to 2.144 ps for Ar). At all state points, the simulation box size is large enough that the finite size does not noticeably affect the density fluctuations. The simulations were equilibrated for 80000 timesteps. During equilibrium, velocity rescaling was performed every 31 timesteps to ensure that equilibrium density inhomogeneities would be established at near-critical state points [H. L. Martinez, R. Ravi, and S. C. Tucker, J. Chem. Phys. 104, 1067 (1996)]. Solute force data was then collected over 500 microcanonical blocks, each 4000 timesteps in length (a total time of 2 000 000 timesteps), with a velocity rescaled equilibrium of 100 timesteps between each block. Such lengthy runs were required for the solute to adequately sample the broad range of slowly fluctuating local environments; see Refs. 4 and 11. Error bars were computed by taking standard deviations over simulation blocks; in all cases these error bars were smaller than the plotting symbols used in Figs. 2(b), 4, and 5.
26. r = 1.01. This difference results because two- and three-dimensional systems are members of different universality classes (Ref. 3).
27. ck, the qualitative trends are invariant to the value used.
28. LJ.
29. Such broad distributions have the potential to generate inhomogeneous broadening effects on vibrational relaxation; G. Goodyear and S. C. Tucker, Proceedings of the 1998 NATO ASI on Supercritical Fluids, Kemer, Turkey, and in preparation.
30. In the absence of critical fluctuations at very low densities, one may still see short-length-scale density inhomogeneities due to intermolecular forces. Such fluctuations generally give rise only to first solvation shell local density enhancement effects.
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32. 1(ρ, T).