Local structural effects on low-frequency vibrational spectrum of liquid water: The instantaneous-normal-mode analysis

Tsai, K. H.; Wu, Ten-Ming

doi:10.1016/j.cplett.2005.10.067

Cited by 23 publications

(18 citation statements)

References 27 publications

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“…According to the literature [77][78][79][80][81][82][83] , the designation for the low frequency band in the Raman spectrum of liquid water observed experimentally at about 60 cm -1 is still a subject of debate; however it is now accepted that the presence of this band is due to a mixture of underlying mechanisms, including hydrogen bridge bonds and cage effects. The shoulder observed at higher frequencies for the average spectral density…”

Section: E Atomic Translational Dynamics -Spectral Densitiesmentioning

confidence: 99%

Hydrogen Bonding and Related Properties in Liquid Water: A Car–Parrinello Molecular Dynamics Simulation Study

2014

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The local hydrogen bonding structure and dynamics of liquid water have been investigated using the Car-Parrinello molecular dynamics simulation technique. The radial distribution functions and coordination numbers around water molecules have been found to be strongly dependent on the number of hydrogen bonds formed by each molecule, revealing also the existence of local structural heterogeneities in the structure of the liquid. The results obtained have also revealed the strong effect of the local hydrogen bonding network on the local tetrahedral structure and entropy. The investigation of the dynamics of the local hydrogen bonding network in liquid water has shown that this network is very labile and the hydrogen bonds break and reform very rapidly. Nevertheless, it has been found that the hydrogen bonding states associated with the formation of 4 hydrogen bonds by a water molecule exhibit the largest survival probability and corresponding lifetime. The reorientational motions of water molecules have also been found to be strongly dependent on their initial hydrogen bonding state.Finally the dependence of the librational and vibrational modes of water molecules on the local hydrogen bonding network has been carefully examined, revealing a significant effect upon the libration and bond-stretching peak frequencies. The calculated low frequency peaks come in agreement with previously reported interpretations of the experimental low frequency Raman spectrum of liquid water.

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Section: E Atomic Translational Dynamics -Spectral Densitiesmentioning

confidence: 99%

Hydrogen Bonding and Related Properties in Liquid Water: A Car–Parrinello Molecular Dynamics Simulation Study

2014

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“…[12,13] Thus, it is widely accepted that the bend band is partially associated with hydrogen bonds and to the effects of the local surrounding structure. [9] The stretching band is considered to consist of both the symmetric and asymmetric stretching modes, although no experimental Raman spectroscopy evidence of the former has been published in literature. The symmetric stretch mode is predicted to be polarised while the asymmetric stretch mode is not, thus the weak polarisation of the stretching band must necessarily contain some contribution from a symmetric stretch mode.…”

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confidence: 99%

“…It is now accepted that the modes in this region are due to a mixture of underlying mechanisms, including hydrogen bridge bonds and cage (local structure) effects. [9] The second mode in the bend band was originally assigned as a result of the bifurcation of the hydrogen bond levels, [8,10,11] referred to herein as the torsion mode. [5] The origin of the bend band has been discussed in detail as caused by the strong, directional hydrogen bond network, which makes bands intense and sharp, but it alone cannot account for the transverse dynamics measured.…”

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confidence: 99%

The Extreme Low‐Frequency Raman Spectrum of Liquid Water

Galvin

Zerulla

2011

ChemPhysChem

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“…65, the structures of the simulated liquids were analyzed using two methods: Voronoi tessellation 79 and H-bond configuration. As in our previous studies, [65][66][67] the molecules in a configuration were classified into either four Voronoi groups (VGs) according to the asphericity of the Voronoi polyhedron associated with each molecule 80 or ten H-bond configurations. In each type of classification, a subensemble consisted of molecules belonging to a VG or with the same H-bond configuration.…”

Section: Model Simulation and Subensemblementioning

confidence: 99%

“…Second, we classified water molecules into subensembles according to their local environments and the rotational stable-INM spectra of these subensembles were calculated. [65][66][67] Using the rotational stable-INM spectra of these subensembles, we could, therefore, examine the localstructure effects on the OH-bond orientational TCFs of water. The second-cumulant predictions, which were calculated using either the AVAF power spectra or the rotational stable-INM spectra, for the OH-bond orientational TCFs were highly consistent with the simulation results on short timescales.…”

Section: Introductionmentioning

confidence: 99%

Local structural effects on orientational relaxation of OH-bond in liquid water over short to intermediate timescales

Lin

Tang

2014

The Journal of Chemical Physics

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By simulating the rigid simple point charge extended model at temperature T = 300 K, the orientational relaxation of the OH-bond in water was investigated over short to intermediate timescales, within which molecules undergo inertial rotation and libration and then enter the rotational diffusion regime. According to the second-cumulant approximation, the orientational time correlation function (TCF) of each axis that is parallel or perpendicular to an OH-bond is related to an effective rotational density of states (DOS), which is determined using the power spectra of angular velocity autocorrelation functions (AVAFs) of the other two axes. In addition, the AVAF power spectrum of an axis was approximated as the rotational stable instantaneous normal mode (INM) spectrum of the axis. As described in a previous study [S. L. Chang, T. M. Wu, and C. Y. Mou, J. Chem. Phys. 121, 3605 (2004)], simulated molecules were classified into subensembles, according to either the local structures or the H-bond configurations of the molecules. For global molecules and the classified subensembles, the simulation results for the first- and second-rank orientational TCFs were compared with the second-cumulant predictions obtained using the effective rotational DOSs and the rotational stable-INM spectra. On short timescales, the OH-bond in water behaves similar to an inertial rotor and its anisotropy is lower than that of a water molecule. For molecules with three or more H-bonds, the OH-bond orientational TCFs are characterized by a recurrence, which is an indication for libration of the OH-bond. The recurrence can generally be described by the second-cumulant prediction obtained using the rotational stable-INM spectra; however, the orientational TCFs after the recurrence switch to a behavior similar to that predicted using the AVAF power spectra. By contrast, the OH-bond orientational TCFs of molecules initially connected with one or two H-bonds decay monotonically or exhibit a weak recurrence, indicating rapid relaxation into the rotational diffusion regime after the initial Gaussian decay. In addition to accurately describing the Gaussian decay, the second-cumulant predictions formulated using the rotational stable-INM spectra and the AVAF power spectra serve as the upper and lower limits, respectively, for the OH-bond orientational TCFs of these molecules after the Gaussian decay.

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Local structural effects on low-frequency vibrational spectrum of liquid water: The instantaneous-normal-mode analysis

Cited by 23 publications

References 27 publications

Hydrogen Bonding and Related Properties in Liquid Water: A Car–Parrinello Molecular Dynamics Simulation Study

Hydrogen Bonding and Related Properties in Liquid Water: A Car–Parrinello Molecular Dynamics Simulation Study

The Extreme Low‐Frequency Raman Spectrum of Liquid Water

Local structural effects on orientational relaxation of OH-bond in liquid water over short to intermediate timescales

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