Instantaneous normal mode analysis of orientational motions in liquid water: Local structural effects

Chang, S. L.; Wu, Ten-Ming; Mou, Chung‐Yuan

doi:10.1063/1.1772759

Cited by 26 publications

(52 citation statements)

References 48 publications

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“…Here, the motion occurs on a harmonic potential. The frequencies extracted from the data are in the range of Ϸ400 cm Ϫ1 , and are qualitatively consistent with instantaneous normal mode analyses of water that show a broad band caused by rotational and translational motions extending from 0 cm Ϫ1 to Ͼ900 cm Ϫ1 (21,22). An important aspect of the results is that, at lower temperatures, the magnitude of the inertial component becomes frequency-independent; at low temperatures the inertial motion does not depend on the strength of the O-DOO hydrogen bond.…”

supporting

confidence: 60%

“…If the potential is dominated by only these two bonds, the result would be a correlation between the OD stretch frequency and the amplitude of the inertial decay. Recent instantaneous normal mode studies provide support for this interpretation, finding that the two donated hydrogen bonds determine the nature of the intermolecular potential energy surface almost entirely (22).…”

Section: Resultsmentioning

confidence: 76%

See 1 more Smart Citation

Water inertial reorientation: Hydrogen bond strength and the angular potential

Moilanen

Fenn

Lin

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

177

314

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The short-time orientational relaxation of water is studied by ultrafast infrared pump-probe spectroscopy of the hydroxyl stretching mode (OD of dilute HOD in H2O). The anisotropy decay displays a sharp drop at very short times caused by inertial orientational motion, followed by a much slower decay that fully randomizes the orientation. Investigation of temperatures from 1°C to 65°C shows that the amplitude of the inertial component (extent of inertial angular displacement) depends strongly on the stretching frequency of the OD oscillator at higher temperatures, although the slow component is frequency-independent. The inertial component becomes frequency-independent at low temperatures. At high temperatures there is a correlation between the amplitude of the inertial decay and the strength of the O-DOO hydrogen bond, but at low temperatures the correlation disappears, showing that a single hydrogen bond (ODOO) is no longer a significant determinant of the inertial angular motion. It is suggested that the loss of correlation at lower temperatures is caused by the increased importance of collective effects of the extended hydrogen bonding network. By using a new harmonic cone model, the experimentally measured amplitudes of the inertial decays yield estimates of the characteristic frequencies of the intermolecular angular potential for various strengths of hydrogen bonds. The frequencies are in the range of Ϸ400 cm ؊1 . A comparison with recent molecular dynamics simulations employing the simple point charge-extended water model at room temperature shows that the simulations qualitatively reflect the correlation between the inertial decay and the OD stretching frequency.ultrafast IR experiments ͉ dynamics ͉ motion ͉ MD simulations ͉ harmonic model A lthough a great deal is known about water's bulk thermodynamic properties, the complex intermolecular forces that govern its nanoscopic structural arrangements and dynamics have made a detailed picture of the instantaneous local structures of water and their evolution elusive. Numerous models for the structure of water have been proposed to account for its anomalous behavior at different temperatures and pressures (1-6). These models all have some degree of success in reproducing the observed radial distribution function and other properties of water.Here, we present results on the fast, local (inertial) angular motions of dilute HOD molecules in water within their initial hydrogen-bonding structure through a study of how the orientational motions of water depend on the OD stretching frequency and temperature. The short-time orientational motions of the HOD molecule depend on the potential energy surface established by neighboring water molecules. Measurements of the orientational relaxation as a function of OD stretching frequency and temperature provide insight into how the motions of the HOD molecule depend on the strength of the O-DOO hydrogen bond (nature of the potential energy surface) and how the local structure of water changes with temperature. The measurem...

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supporting

confidence: 60%

Section: Resultsmentioning

confidence: 76%

Water inertial reorientation: Hydrogen bond strength and the angular potential

Moilanen

Fenn

Lin

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

177

314

View full text Add to dashboard Cite

show abstract

“…While D trans (ω) and D rot (ω) dominate the low-and highfrequency regimes, respectively, D stretch (ω) is significant only around the extremely high frequency of 3600 cm −1 for the O-H stretching. These features are consistent with those of the modified FSPC model [21] and the rigid SPC/E model [60], where the latter has only D trans (ω) and D rot (ω). The general evidence that the low-(high-) frequency modes are more extended (localized) indicates that the translational (rotational) modes are more extended (localized).…”

Section: A Vibrational Density Of States Of Watersupporting

confidence: 86%

Localization-delocalization transition of the instantaneous normal modes of liquid water

Huang

Chang

2013

Phys. Rev. E

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Despite the fact that the localization-delocalization transition (LDT) widely exists in wave systems, quantitative studies on its critical and multifractal properties are mainly focused on solids. In this work, these properties are investigated on the vibrational motions of liquid water. Simulations of up to 18000 molecules on the flexible extended simple point charge water model provide nearly 10(6) instantaneous normal modes. They are shown to undergo an LDT close to the translational transition and exhibit multifractal fluctuations while approaching the LDT. In combination with finite-size scaling, multifractal analysis predicts the critical frequency Im(ω(c))≈-131.6 cm(-1) for unstable modes at room temperature. The estimated critical exponent ν≈1.60 is close to those of other calculated systems in the same Wigner-Dyson class. At the LDT, the fractal spectrum f(α) and the most probable local vibrational intensity α(mc)≈4.04 coincide with those of the Anderson model, which might be additional universal properties of LDT in more general wave systems. The results extend the validity of the multifractal scaling approach beyond Andersonian systems to a Hessian system.

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“…Corcelli and Skinner have produced simulated IR and Raman O-H stretch spectra from ab initio calculations that agree well qualitatively with experiment [86]. Using ab initio-based approximations to calculate infrared spectra from molecular dynamics simulations (Instantaneous Normal Mode Analysis), infrared spectra of aqueous solutions have been simulated with surprising accuracy for a variety of systems [87–89]. Calculations of spectra from molecular dynamics simulations of TIP3P, TIP4P, and SPC/E [90] models have all produced simulated spectra that agree well with experiment for both linear IR O-H stretch spectra as well as nonlinear IR measurements [91–93].…”

Section: Discussionmentioning

confidence: 99%

Effects of salts of the Hofmeister series on the hydrogen bond network of water

Nucci

Vanderkooi

2008

Journal of Molecular Liquids

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The effect of salts on water behavior has been a topic of interest for many years; however, some recent reports have suggested that ions do not influence the hydrogen bonding behavior of water. Using an effective two-state hydrogen bonding model to interpret the temperature excursion infrared response of the O-H stretch of aqueous salt solutions, we show a strong correlation between salt effects on water hydrogen bonding and the Hofmeister order. These data clearly show that salts do have a measurable impact on the equilibrium hydrogen bonding behavior of water and support models which explain Hofmeister effects on the basis of solute charge density.

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Instantaneous normal mode analysis of orientational motions in liquid water: Local structural effects

Cited by 26 publications

References 48 publications

Water inertial reorientation: Hydrogen bond strength and the angular potential

Water inertial reorientation: Hydrogen bond strength and the angular potential

Localization-delocalization transition of the instantaneous normal modes of liquid water

Effects of salts of the Hofmeister series on the hydrogen bond network of water

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