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Volumn 112, Issue 45, 2008, Pages 14230-14242

On the molecular mechanism of water reorientation

Author keywords

[No Author keywords available]

Indexed keywords

DYNAMICS; HYDROGEN; IMAGE SEGMENTATION; MOLECULAR DYNAMICS; QUANTUM CHEMISTRY; RATE CONSTANTS; REACTION KINETICS;

EID: 57049116557     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp805217u     Document Type: Article
Times cited : (397)

References (112)
  • 2
    • 25444514520 scopus 로고    scopus 로고
    • Bagchi, B. Chem. Rev. 2005, 105, 3197-3219.
    • (2005) Chem. Rev , vol.105 , pp. 3197-3219
    • Bagchi, B.1
  • 20
    • 0004240239 scopus 로고
    • The Chemical Catalog Company: New York
    • Debye, P. Polar Molecules; The Chemical Catalog Company: New York, 1929.
    • (1929) Polar Molecules
    • Debye, P.1
  • 22
    • 84906406412 scopus 로고    scopus 로고
    • In the analysis of experiments, the Debye diffusional model is often combined via the Einstein relation between the diffusion constant and the friction constant and a hydrodynamic model for the friction constant to produce the Debye-Stokes-Einstein relation in which DR is inversely proportional to the solvent viscosity. The relationship between the rotational friction and the viscosity is logically distinct from eq 2, as already noted by Debye.20
    • 20
  • 29
    • 84906391782 scopus 로고    scopus 로고
    • The rearrangement of the environment also involves the orientation of the Ob water with respect to O*H*, which is initially random and evolves to the proper configuration to receive a H-bond from H*, where the two hydrogens on Ob point away from H*
    • b point away from H*.
  • 30
    • 84906391780 scopus 로고    scopus 로고
    • We note that this mechanism evidences that in liquid water, large-amplitude rotations are coupled with translational motion since the reorientation involves an exchange of water molecules within the first shell of O*. The jump reorientation mechanism is therefore likely to be also intrinsically related to translational motion in water, a topic under investigation Laage, D, Møller, K. B, Hynes, J. T. in progress
    • We note that this mechanism evidences that in liquid water, large-amplitude rotations are coupled with translational motion since the reorientation involves an exchange of water molecules within the first shell of O*. The jump reorientation mechanism is therefore likely to be also intrinsically related to translational motion in water, a topic under investigation (Laage, D.; Møller, K. B.; Hynes, J. T. in progress).
  • 40
    • 84906377598 scopus 로고    scopus 로고
    • Ponder, J. W. TINKER: Software Tools for Molecular Design, v 4.2; Washington University School of Medecine: Saint Louis, MO, 2004.
    • Ponder, J. W. TINKER: Software Tools for Molecular Design, v 4.2; Washington University School of Medecine: Saint Louis, MO, 2004.
  • 42
    • 84906406408 scopus 로고    scopus 로고
    • In addition, first-principles MD techniques suffer from a high computational cost, limiting the trajectory length to a few tens of picoseconds with a simulation box of a few hundred atoms, which is not sufficient here, and the simple DFT functional employed in these simulations is well known to lead to overstructured water.108
    • 108
  • 44
    • 84906406409 scopus 로고    scopus 로고
    • We stress that this moderate frequency dependence of the jump probability should have only a limited impact on the reorientation. Indeed, the higher jump probability applies only as long as the delay between the excitation pulse and the jump is shorter than the frequency decorrelation time of approximately <1.5 ps,109 and at these short delays, the strong frequency dependence of the initial (<200 fs) librational reorientation is already present.43
    • 43
  • 48
    • 84906363260 scopus 로고    scopus 로고
    • 15 with no bifurcated H-bond in the transition-state structure.
    • 15 with no bifurcated H-bond in the transition-state structure.
  • 59
    • 84906377597 scopus 로고    scopus 로고
    • Our attention has been recently drawn to previous work by O'Reilly which had already suggested, in part motivated by certain unpublished trajectory results of Stillinger and Rahman, that water reorientation occurs through large-amplitude jumps and had used the Ivanov model to determine the reorientation time τ2-17 However, ref 17 assumes that the angular jumps are caused by hard-sphere collisions and that the free-energy barrier lies along the angular coordinate; this is in clear contrast with the H-bond-centered picture we describe here, where, as detailed in section 4.2, the rate-limiting step is the rearrangement of the environment. In addition, no frame reorientation between the jumps is considered in ref 17
    • 17 However, ref 17 assumes that the angular jumps are caused by hard-sphere collisions and that the free-energy barrier lies along the angular coordinate; this is in clear contrast with the H-bond-centered picture we describe here, where, as detailed in section 4.2, the rate-limiting step is the rearrangement of the environment. In addition, no frame reorientation between the jumps is considered in ref 17.
  • 60
    • 0000925532 scopus 로고
    • The Theory of Reactions in Solution
    • Baer, M, Ed, CRC Press: Boca Raton, FL
    • Hynes, J. T. The Theory of Reactions in Solution. In Theory of Chemical Reaction Dynamics; Baer, M., Ed.; CRC Press: Boca Raton, FL, 1985; pp 171-234.
    • (1985) Theory of Chemical Reaction Dynamics , pp. 171-234
    • Hynes, J.T.1
  • 63
    • 84906363261 scopus 로고    scopus 로고
    • 62 since a H-bond exchange can occur before the reorienting water has left the ion hydration shell.
    • 62 since a H-bond exchange can occur before the reorienting water has left the ion hydration shell.
  • 66
    • 0034504583 scopus 로고    scopus 로고
    • Luzar, A. J. Chem. Phys. 2000, 113, 10663-10675.
    • (2000) J. Chem. Phys , vol.113 , pp. 10663-10675
    • Luzar, A.1
  • 84
    • 84906363262 scopus 로고    scopus 로고
    • 3 time has not been performed yet, but promising time-resolved hyper-Rayleigh scattering techniques should allow its determination for water in the near future (T. Buckup, private communication).
    • 3 time has not been performed yet, but promising time-resolved hyper-Rayleigh scattering techniques should allow its determination for water in the near future (T. Buckup, private communication).
  • 85
    • 84906391779 scopus 로고    scopus 로고
    • jump〉 is then close to 56°.
    • jump〉 is then close to 56°.
  • 92
    • 84906363263 scopus 로고    scopus 로고
    • 2 are therefore similar.
    • 2 are therefore similar.
  • 94
    • 84906406407 scopus 로고    scopus 로고
    • The measured 2-3 kcal/mol activation energy for the proton mobility in water10 is compatible with the activation energy that we determine for water reorientation
    • 10 is compatible with the activation energy that we determine for water reorientation.
  • 96
    • 84906391777 scopus 로고    scopus 로고
    • The OH rotation quantization slightly alters the activation free energy from the classical approximation discussed in section 4.2; we ignore this in the present work
    • The OH rotation quantization slightly alters the activation free energy from the classical approximation discussed in section 4.2; we ignore this in the present work.
  • 103
    • 84906391778 scopus 로고    scopus 로고
    • The special character of the angular versus translational diffusion model has, for example, been recognized in ref 23
    • The special character of the angular versus translational diffusion model has, for example, been recognized in ref 23.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.