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Volumn 100, Issue 4, 1996, Pages 1266-1282

Short-time dynamics of solvation: relationship between polar and nonpolar solvation

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EID: 33748625353     PISSN: 00223654     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp951326a     Document Type: Article
Times cited : (176)

References (139)
  • 16
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    • Simon, J. D., Ed.; Kluwer. Dordrecht, The Netherlands
    • Hynes, J. T. In Ultrafast Dynamics of Chemical Systems; Simon, J. D., Ed.; Kluwer. Dordrecht, The Netherlands, 1994; p 345.
    • (1994) Ultrafast Dynamics of Chemical Systems , pp. 345
    • Hynes, J.T.1
  • 61
    • 85033047509 scopus 로고    scopus 로고
    • submitted for publication. The ultrafast dynamics in these nonpolar solvents appears to be strikingly similar to that seen in dipolar solvents.
    • The first time-resolved-fluorescence solvation dynamics experiments in nonpolar solvents comparable in time resolution to those conducted in dipolar solvents have recently been reported: Gardecki, J.; Horng, M. L.; Papazyan, A.; Maroncelli, M. J. Mol. Liq., submitted for publication. The ultrafast dynamics in these nonpolar solvents appears to be strikingly similar to that seen in dipolar solvents.
    • J. Mol. Liq.
    • Gardecki, J.1    Horng, M.L.2    Papazyan, A.3    Maroncelli, M.4
  • 75
    • 5844256546 scopus 로고
    • Szudy, J., Ed.; Ossolineum: Wroclaw, Poland
    • Seeley, G.; Keyes, T. In Spectral Une Shapes; Szudy, J., Ed.; Ossolineum: Wroclaw, Poland, 1989; Vol. 5, p 649.
    • (1989) Spectral Une Shapes , vol.5 , pp. 649
    • Seeley, G.1    Keyes, T.2
  • 115
    • 85033058887 scopus 로고    scopus 로고
    • note
    • For optical time-resolved emission and transient-absorption studies, the spectroscopically relevant interaction A should be regarded as the difference between the solute-solvent interaction with the solute in its ground electronic state and the solute-solvent interaction with the solute in some electronically excited state. We shall refer to this difference as the "differential solute-solvent interaction".
  • 120
    • 85033062610 scopus 로고    scopus 로고
    • note
    • The assumption of a frozen solute will usually be quite satisfactory for the kinds of time scales under consideration here, but it is straightforward to transcend this approximation if we so desire. We shall return to this issue in section VI.
  • 121
    • 84923004214 scopus 로고
    • Clarendon Press: Oxford, U.K., Chapter 2. Such multipole expansions are closely related to the rotationally invariant expansions commonly used in studying liquids with electrostatic interactions. See, for example: Friedman, H. L. A Course in Statistical Mechanics; Prentice Hall: Englewood Cliffs, NJ, 1985; Chapter 8 and Appendix 2.
    • Gray, C. G.; Gubbins, K. E. Theory of Molecular Fluids; Clarendon Press: Oxford, U.K., 1984; Chapter 2. Such multipole expansions are closely related to the rotationally invariant expansions commonly used in studying liquids with electrostatic interactions. See, for example: Friedman, H. L. A Course in Statistical Mechanics; Prentice Hall: Englewood Cliffs, NJ, 1985; Chapter 8 and Appendix 2.
    • (1984) Theory of Molecular Fluids
    • Gray, C.G.1    Gubbins, K.E.2
  • 122
    • 0003556249 scopus 로고
    • Here we adopt the definition of the quadrupole moment given on pp 839-840, leading to a quadrupolequadrupole interaction of the form shown on
    • Hirschfelder, J. O.; Curtiss, C. F.; Bird, R. B. Molecular Tlieory of Gases and Liquids; Wiley: New York, 1954. Here we adopt the definition of the quadrupole moment given on pp 839-840, leading to a quadrupolequadrupole interaction of the form shown on p 27.
    • (1954) Molecular Tlieory of Gases and Liquids; Wiley: New York , pp. 27
    • Hirschfelder, J.O.1    Curtiss, C.F.2    Bird, R.B.3
  • 123
    • 85033056561 scopus 로고    scopus 로고
    • note
    • 2, the mean-square fluctuation in the solute-solvent interaction. A formula somewhat more accurate for polar solvents may be that of van der Zwan and Hynes, 61 which predicts that this simple free-rotation result for the square solvation frequency should be multiplied by a dielectric-constant-containing factor. This factor is close to 1 for nonpolar solvents but can be significant in dipolar cases.
  • 124
    • 85033053423 scopus 로고    scopus 로고
    • note
    • Tetrahedral and octahedral molecules are the obvious exceptions.
  • 131
    • 85033036317 scopus 로고    scopus 로고
    • note
    • Both liquids were studied under near-triple point conditions, but we should point out that the thermodynamic states may not be precisely equivalent.
  • 132
    • 85033072491 scopus 로고    scopus 로고
    • note
    • Indeed, there is simulation evidence that points in precisely this direction. In an aqueous environment, both formaldehyde78 and solvated electrons79 seem to be solvated via translational motion of water in the first solvation shell.
  • 136
    • 85033043266 scopus 로고    scopus 로고
    • note
    • -1. Though this same dielectric correction is unlikely to be appropriate for nonpolar solvents, for completeness we note that if it were applied to the analogous solvation frequency for COi, it would result in less than a 1% change.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.