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Volumn 109, Issue 1, 2005, Pages 44-56

Anomalous Microscopic Dielectric Response of Dipolar Solvents and Water

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE REDISTRIBUTION; DIELECTRIC GEOMETRIES; POLARIZATION FLUCTUATIONS; SPATIAL CORRELATORS;

EID: 12344305383     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp047091x     Document Type: Article
Times cited : (13)

References (136)
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    • Silverman R. A., Ed; Prentice Hall: Englewood Cliffs, NJ, References 75 and 76
    • Time-dependent dielectric properties are more complex, because they are determined by a larger number of statistical variables, velocities, and coordinates (in other words, by temporal and spatial dispersion of solvent), while static properties are determined by coordinates only (spatial dispersion). Abrikosov, A. A.; Gorkov, I. E.; Dzyaloshinski, I. E. Methods of quantum field theory in statistical physics; Silverman R. A., Ed; Prentice Hall: Englewood Cliffs, NJ, 1963. References 75 and 76.
    • (1963) Methods of Quantum Field Theory in Statistical Physics
    • Abrikosov, A.A.1    Gorkov, I.E.2    Dzyaloshinski, I.E.3
  • 56
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    • note
    • 11,26 are not surprising, because the model was developed for dipolar materials only.
  • 57
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    • Dogonadze, R. R., Kalman, E., Komyshev, A. A., Ulstrup, J., Eds; Elsevier Amsterdam
    • Kornyshev, A. A. In The Chemical Physics of Salvation; Dogonadze, R. R., Kalman, E., Komyshev, A. A., Ulstrup, J., Eds; Elsevier Amsterdam, 1985; p 77.
    • (1985) The Chemical Physics of Salvation , pp. 77
    • Kornyshev, A.A.1
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    • note
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    • Kornyshev, A. A.: Leikin, S.; Sutmann, G. Electrochim. Acta 1997, 42, 849. Medvedev, I. G. Electrochim. Acta 2004, 49, 207.
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    • Medvedev, I.G.1
  • 108
    • 12344306012 scopus 로고    scopus 로고
    • note
    • PF can also accept an H-bond in H-bonding solvents. According to our quantum chemical calculations, such a bond may slightly reduce the Stokes shift and the reorganization energy (Supporting Information, Section 1.7S). Such a bond should be sterically less favorable in N-methyl formamide, explaining its proximity to the non-H-bonding solvents in Figure 2.
  • 109
    • 0033217726 scopus 로고    scopus 로고
    • 116 Similar to free PF in water, cosolvents rapidly destroy the anomaly for the bound dye. This effect does not seem to be related to cosolvent adsorption (no cosolvent adsorption to the surface of this protein was observed, Topolev, V. V.; Krishtalik, L. I. Biofizika 1999, 44, 992-995) or to a change in the protein conformation, Khurgin, I. I.; Azizov, I. M.; Abaturov, L. V.; Kogan, G. A.; Rosliakov, V. I. Biofizika 1972, 17, 390-395. A detailed account of the cosolvent effect will be published elsewhere.
    • (1999) Biofizika , vol.44 , pp. 992-995
    • Topolev, V.V.1    Krishtalik, L.I.2
  • 110
    • 0015345488 scopus 로고
    • 116 Similar to free PF in water, cosolvents rapidly destroy the anomaly for the bound dye. This effect does not seem to be related to cosolvent adsorption (no cosolvent adsorption to the surface of this protein was observed, Topolev, V. V.; Krishtalik, L. I. Biofizika 1999, 44, 992-995) or to a change in the protein conformation, Khurgin, I. I.; Azizov, I. M.; Abaturov, L. V.; Kogan, G. A.; Rosliakov, V. I. Biofizika 1972, 17, 390-395. A detailed account of the cosolvent effect will be published elsewhere.
    • (1972) Biofizika , vol.17 , pp. 390-395
    • Khurgin, I.I.1    Azizov, I.M.2    Abaturov, L.V.3    Kogan, G.A.4    Rosliakov, V.I.5
  • 112
    • 12344323344 scopus 로고    scopus 로고
    • note
    • 2 ≈ 12, on the basis of the gas-phase TD/MPW1PW1/6-31G(d,p) calculation and the similarity of the sizes of these probes.
  • 114
    • 12344270774 scopus 로고    scopus 로고
    • note
    • st) only, 2-4 charges corresponding to the largest atomic charges in a polarizable oblate spheroid cavity can be used for C153 and PF instead.
  • 117
    • 12344268676 scopus 로고    scopus 로고
    • note
    • c ≈ 2.5). This is the case for acetonitrile analyzed in ref 9.
  • 118
    • 12344287820 scopus 로고    scopus 로고
    • note
    • It follows from the response theory that equilibrium density changes in response to static electric field are identically zero for the linear response of a solvent whose electrically neutral molecules have antisymmetric charge density and symmetric nonelectrostatic potential with respect to the molecule center (e.g., a dipole inside a sphere), because the density change in such a solvent may not depend on inversion of the electric field direction. For asymmetric solvent molecules, linear density changes are not forbidden.
  • 121
    • 12344294356 scopus 로고    scopus 로고
    • note
    • s for AO in water is also accompanied by an anomalous solvent isotope effect. This effect is not observed in methanol.
  • 123
    • 12344336218 scopus 로고    scopus 로고
    • note
    • 30 We also found similar sensitivity for the specular reflection model. Thus, all these heuristic models are in qualitative disagreement with the data.
  • 124
    • 12344249483 scopus 로고    scopus 로고
    • note
    • 30 It is unclear whether such energies containing significant nondielectric contributions from ion-solvent electron donor-acceptor interactions and from the solvent pre-existing potential can be described in terms of the solvent dielectric properties. Furthermore, the fitting function directly couples changes in solute cavity size to solute charge. We are not aware of any indication that such direct interaction between solute electric field and mass (solvent density near solute) is important. In contrast, such coupling, if it exists, seems to be insignificant for our probe, because the measured reorganization energies are almost insensitive to pressure; Sections 4.1 and 5.
  • 134
    • 12344312946 scopus 로고    scopus 로고
    • note
    • 108 The absence of an anomalous response for C153 may be explained (e.g., assuming that anomalous polarization fluctuations occur at 1-2.5 Å length scales, which is within the range of charge redistribution of PF and outside the range of C153).
  • 135
    • 12344284617 scopus 로고    scopus 로고
    • note
    • 1.
  • 136
    • 12344323343 scopus 로고    scopus 로고
    • note
    • 2Co). We verified that the inclusion of these generated data into the analysis presented in Table 1 would produce similar results.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.