-
15
-
-
84913185643
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-
Several of the more complete studies during this period are Refs. 12-14.
-
-
-
-
30
-
-
84913185642
-
-
L only for the response to a charge perturbation. However, the time constant appropriate to other solute multipole changes are similar and the distinction is not important here. See also the discussion in Refs. 23 and 85.
-
-
-
-
32
-
-
0024736142
-
-
Discussions of the physical content of this longitudinal relaxation time and what distinguishes it from the (transverse) dielectric relaxation time can be found in
-
(1989)
J. Phys. Chem.
, vol.93
, pp. 7026
-
-
Kivelson1
Friedman2
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38
-
-
84913185641
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-
S. J. Rosenthal, X. Xie, M. Du, and G .R. Fleming, submitted to J. Chem. Phys.
-
-
-
-
40
-
-
84913185640
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-
C. F. Chapman and M. Maroncelli, “On the Solute Dependence of Solvation Dynamics”, manuscript in preparation.
-
-
-
-
41
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-
84913185639
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-
C. F. Chapman, R. S. Fee, and M. Maroncelli, unpublished results.
-
-
-
-
42
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-
84913185638
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-
R. S. Fee and M. Maroncelli, “Solvation Dynamics in Alcohols,” manuscript in preparation.
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-
-
-
57
-
-
0001375091
-
Solvation Dynamics Studied by Picosecond Fluorescence: Microscopic Reorientation and Longitudinal Relaxation of the Solvent
-
(1990)
Laser Chemistry
, vol.10
, pp. 413
-
-
Declemy1
Rulliere2
Kottis3
-
60
-
-
84913185636
-
-
b R. Richert and A. Wagener, submitted to J. Phys. Chem.
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-
-
-
65
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-
84913185635
-
-
Spectral changes can of course also arise from various excited-state reactions which may confuse the interpretation of spectral shifts. Some probe molecules used in early studies did actually suffer from this problem. See for example the recent reinvestigation of the LDS-750 probe in alcohol solvents: S. Blanchard, J. Chem. Phys., in press.
-
-
-
-
70
-
-
0011259348
-
-
This effect has been observed for some highly polar molecules in their ground states. See for example, Faraday Trans. I
-
(1980)
J. Chem. Soc.
, vol.76
, pp. 43
-
-
Pawelka1
Sobczyk2
-
71
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-
84913185633
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-
a H. J. Kim and J. T. Hynes, manuscript in preparation
-
-
-
-
75
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-
84913185632
-
-
3 effect on radiative rates rather than to electronic changes.
-
-
-
-
78
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-
84913185631
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-
b R. Richert and A. Wagener, submitted to J. Phys. Chem.
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-
-
-
82
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-
84913185630
-
-
The resolutions quoted here are reported or estimated values of the FWHMof the instrument response function.
-
-
-
-
83
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-
84913185629
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-
a H. J. Kim and J. T. Hynes, manuscript in preparation
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-
-
-
84
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-
84913185628
-
-
0=10 would generally be farther from the high frequency limit than these values indicate.
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-
-
-
92
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-
84913185627
-
-
From fits to the temperature-dependent data compiled in Ref. 27.
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-
-
-
95
-
-
84913183867
-
-
v is ∼7.
-
-
-
-
107
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-
84913183866
-
-
L for a Debye solvent) independent of solute shape or charge distribution.
-
-
-
-
116
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84913183865
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-
b I. Rips, J. Klafter and J. Jortner, J. Phys. Chem. 89, 4288
-
-
-
-
122
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-
84913183864
-
-
“Linear” here refers to the fact that the solvent polarization is directly proportional to the solute charge or dipole moment. Wolynes [87] also noted that the approach taken in the “dynamical MSA” theory could in principle be used with any linear equilibrium solvation model and is in no way restricted to the MSA solution.
-
-
-
-
124
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-
84913183863
-
-
There is currently some disagreement concerning this field factor. As discussed by Ranieri et al. [93] some authors use sin(ka)/ka while ethers use &{π/2-Si(ka)&} for the transform of an ionic field (Si is the sine integral). In the text and calculations displayed here we have followed the choice of Rainieri et al.
-
-
-
-
125
-
-
84913183862
-
-
For a general discussion of the meaning of this dielectric response function see Refs. 82 and 96.
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-
-
-
128
-
-
0002547850
-
Computer simulation and the dielectric constant at finite wavelength
-
(1986)
Molecular Physics
, vol.57
, pp. 97
-
-
Neumann1
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140
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-
84913183861
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-
R. S. Fee, J. A. Milsom and M. Maroncelli, J. Phys. Chem. 96, 000.
-
-
-
-
142
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-
84913183860
-
-
Note that both the “dynamical MSA” [87–90] and the Chandra and Bagchi [99] and Fried and MukameI [110] treatments utilize analytical results available at the MSA level of theory for a dipolar hard sphere fluid. The two uses are not identical however. The DMSA theory relies on the equilibrium MSA solution for the structure of a hard sphere solute immersed in a dipolar hard sphere solvent whereas in the latter theories it is only the MSA solution for the pure solvent that is employed.
-
-
-
-
143
-
-
84913183859
-
-
0 and used &{π/2-Si(ka)&} in place of &{sin(ka)/ka&}, however, Eq. 10 is to be preferred over these earlier versions (B. Bagchi, private communications).
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-
-
-
148
-
-
84913183858
-
-
This value is based on comparisons of the van der Waals volumes of a number of common solvents and probes.
-
-
-
-
149
-
-
84913183857
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-
DMSA is found to be 1.0 ± 0.5. However, this “perfect” average comes about with many solvents, in particular those we consider to have the most reliable data, having ratios much less than unity.
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-
-
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154
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-
84913183856
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-
a A. Warshel and W. W. Parsons, Ann. Rev. Phys. Chem. 42, in press
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-
-
-
179
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-
84913183855
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-
R. S. Fee and M. Maroncelli, “Estimating Time Zero in Time-Evolving Fluorescence Spectra,” manuscript in preparation.
-
-
-
-
181
-
-
84913183854
-
-
ΔE(t). To distinguish it from these functions, following Ref. 129 we use the symbol Δ(t) to denote an equilibrium time correlation function (tcf). We note that in statistical mechanics C(t) is conventionally used to designate a tcf, so that this notation is far from ideal. However, given the advanced state of the field the present choice seems a reasonable compromise.
-
-
-
-
182
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-
84913183853
-
-
The discussion here concerns the tcfs in an equilibrium system that form the basis of a linear response treatment of the dynamics. The equivalent “inertial” dynamics in the non-equilibrium response description are dynamics that depend only on the forces imposed by solute-solvent interactions and not on solvent-solvent interactions.
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-
-
-
183
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-
84913183852
-
-
It would be of interest to use the method outlined in Ref. 61 to estimate the fraction of the solvation dynamics missed in water and the other solvents discussed here in order to test whether the extent of fast relaxation predicted from the simulations is correct.
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-
-
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185
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-
84946636446
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Spectroscopic and transport properties of water
-
We note that in the cases of acetonitrile and water, for which a complete ϵ(ω) including the inertial solvent modes has been simulated, use of the full ϵ(ω) as input to even the simple continuum model appears to provide a reasonable description of the solvation dynamics., See Refs. 133 and compare the results in Ref. 121, to Fig. 13 in
-
(1982)
Molecular Physics
, vol.46
, pp. 513
-
-
Impey1
Madden2
McDonald3
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186
-
-
84913183851
-
-
Chandra and Bagchi (Ref. 102) first formulated a theory for inertial effects in solvation dynamics without the inclusion of “viscoclasticity” or frequency-dependent friction. However, in order to obtain the substantial inertial / librational effects observed in simulations, they found it necessary to include the fact that the friction seen by high-frequency motions is much less than the full zero frequency friction (Ref. 103).
-
-
-
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188
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-
84913183850
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b I. Rips, J. Klafter and J. Jortner, J. Phys. Chem. 89, 4288
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-
-
-
189
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-
84913183849
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-
a D. McMorrow and W.T. Lotshaw, Chem. Phys. Lett., in press
-
-
-
-
196
-
-
0002924146
-
-
An overview of the theoretical description of these and related techniques is provided in:
-
(1990)
Ann. Rev. Phys. Chem.
, vol.41
, pp. 647
-
-
Mukamel1
-
201
-
-
84913183848
-
-
A. Chandra and B. Bagchi, “Effects of Solvent Viscoelasticity in the Solvation Dynamics of Ion in a Dense Dipolar Liquid,” submitted to Chem. Phys.
-
-
-
-
203
-
-
84913183847
-
-
b T. A. Betts, A. Papazyan, M. Maroncelli, and F. V. Bright, unpublished results.
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