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Volumn 113, Issue 23, 2000, Pages 10663-10675

Resolving the hydrogen bond dynamics conundrum

Author keywords

[No Author keywords available]

Indexed keywords

COMPUTER SIMULATION; CORRELATION METHODS; FUNCTIONS; MOLECULAR DYNAMICS; RELAXATION PROCESSES; THERMAL EFFECTS; WATER;

EID: 0034504583     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1320826     Document Type: Article
Times cited : (647)

References (69)
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  • 20
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    • (1996) J. Phys. Chem. , vol.100 , pp. 403
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    • T. I. Mizan, P. E. Savage, and R. M. Ziff, J. Comput. Chem. 17, 1757 (1996); J. Phys. Chem. 100, 403 (1996); Innovations in Supercritical Fluids; Science and Technology, in ACS Symposium Series No. 608, edited by K. W. Hutchenson and N. R. Foster (American Chemical Society, Washington, DC, 1995), p. 47.
    • (1995) ACS Symposium Series No. 608 , vol.608 , pp. 47
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    • edited by M. C. Bellissent-Funel and J. C. Dore Kluwer Academic, Dordrecht
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    • The general proof that the long-time limit of a crossing rate is independent of the location of the dividing surface was given by W. H. Miller, Acc. Chem. Res. 9, 306 (1976).
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    • note
    • Note, however, that it is a very difficult task to locate the transition state(s) in complex systems with many degrees of freedom in this way, and what we do is a very crude approximation.
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    • note
    • Arrhenius temperature dependence of rotational relaxation time in water, associated with the fluctuations of hydrogen bonds has been reconfirmed by a recent inelastic coherent neutron scattering at large Q and ω (Teixeira et al., to be reported).
  • 62
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    • can rationalize the differences in observed forms of P(t). Our calculations performed over a broad range of temperatures (Ref. 38), however, do not reveal any significant increase in H bond dynamics correlations at low temperatures, suggesting that the form of P(t) should not change upon moving between different thermodynamic states in the liquid. Furthermore, in the temperature range accessible to real experiments, it has been shown by different techniques (Refs. 1 and 2) that the rotational relaxation time in water is Arrhenius, pointing to the absence of correlations
    • It can be argued that different thermodynamic states in a liquid corresponding to different model potentials [the problem has been nicely reviewed by M. W. Mahanty and W. L. Jorgensen, J. Chem. Phys. 112, 8910 (2000)], can rationalize the differences in observed forms of P(t). Our calculations performed over a broad range of temperatures (Ref. 38), however, do not reveal any significant increase in H bond dynamics correlations at low temperatures, suggesting that the form of P(t) should not change upon moving between different thermodynamic states in the liquid. Furthermore, in the temperature range accessible to real experiments, it has been shown by different techniques (Refs. 1 and 2) that the rotational relaxation time in water is Arrhenius, pointing to the absence of correlations.
    • (2000) J. Chem. Phys. , vol.112 , pp. 8910
    • Mahanty, M.W.1    Jorgensen, W.L.2
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    • Hydration processes in biology
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    • Teixeira, J.1    Luzar, A.2
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    • note
    • The activation free energy at the apparent transition state at T = 298 K is ∼5-6kT, depending on stricter or less strict HB definition (see also Ref. 47).


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