Vibrational dephasing of spherical top anions in aqueous solutions

The vibrational dephasing times for spherical top anions in aqueous solutions calculated from in the shape of the isotropic Raman bands of the fully symmetric vibrations of anions, depending on the temperature and the nature of the anion, are analyzed. It is concluded that the dephasing rates for the anions and their temperature dependences can be reasonably explained within the framework of a model that describes the vibrational dephasing of a diatomic molecule interacting with a solvent molecule by using the Morse potential.     

Vibrational frequency correlation and vibrational dephasing in aqueous nitrate solutions

The vibrational frequency correlation functions

of the v ₁(A′₁) mode of NO₃ ^- ions in aqueous NH₄NO₃ solutions are calculated directly from isotropic Raman profiles, assuming that the process ω(t) is gaussian. The calculated correlation functions are oscillatory decaying functions with a time period of about 0·35 ps. A model based on the generalized Langevin theory is proposed and a theoretical correlation function, obtained by first-order truncation of Mori's continued fraction representation, is found to reproduce both the observed vibrational frequency correlation functions and the vibrational correlation functions. The observed short-time oscillation with a frequency of about 95 cm^-1 is attributed to an inter-molecular librational motion between a NO₃ ^- ion and surrounding water molecules and cations.     

Vibrational relaxation and line widths in liquids dephasing by intermolecular forces

A theory of vibrational relaxation in liquids is presented in which the vibrations are loosely coupled to a bath or lattice of molecular translations and rotations by intermolecular forces. Using the second-order perturbation expressions familiar from magnetic resonance the secular contribution to the line width is calculated. Different coupling paths are considered and expressions given for the line widths in a liquid mixture in terms of number densities and diffusion coefficients valid when reorientation is slow and translation diffusional.     

Proton dynamics in hydrogen-bonded systems

We discuss a simplified version of an ice lattice which consists of an alternating sequence of heavy and light masses. The light masses (protons) are each subject to a bistable potential caused by the heavy masses (oxygens). The protons interact with one another, as do the heavy ions. The interactions between the protons and the oxygens modulate the bistable proton potential. This system is known to exhibit kink and antikink solutions associated with mobile ionic defects accompanied by a lattice distortion. We show that at finite temperatures and in the presence of a constant external field on the protons, the defect velocity is a nonmonotonic function of the temperature, reflecting an interesting interplay of thermal effects (noise) and the constant deterministic external forcing in this nonlinear system. We discuss extensions of the model to higher dimensions, and present preliminary results for the proton motion in such networks.     

Proton dynamics in hydrogen-bonded systems

The proton mean kinetic energy Ke(H) in various systems was calculated between 5 and 320 K using a semi-empirical (SE) approach. The SE calculation relies on the harmonic approximation and decoupling between the various modes, where the input data of the internal and external frequencies were taken from inelastic neutron scattering (INS) and IR/Raman experiments. The studied systems included ordinary H₂O phases, water of crystallisation in sulphate salts, adsorbed water and water confined in various samples of pore dimensions less than 20 Å. These included some zeolites, periodic mesoporous organosilicas (PMOs), beryl, Bikitaite and single- and double-wall carbon nanotubes. All SE calculated Ke(H) values were close to that of pure ice/liquid water, for which a good agreement was found with the deep inelastic neutron scattering (DINS) measurements. However, for water in Beryl at 5 K and ice in carbon nanotubes, at 170 K, large deviations from DINS results were found. Some insight into this problem may be gained by comparing those deviations with recently studied anharmonic systems involving proton double well potentials: Rb₃H(SO₄)₂ and KH₂PO₄, where an excellent agreement was obtained between SE calculations and DINS measurements.     

水在金属表面的氢键网络结构振动谱研究

用从头计算分子动力学模拟方法研究了水在Pt(111)表面上的吸附。总能优化和振动谱分析都表明，在这个表面上水以有序的分子态双层结构存在。这一结论和最近对水在Ru(0001)表面上吸附的计算结果相悖，但和已有的实验相符。此外，文章作者首次确定双层结构中存在两种不同的氢键形式。这两种氢键可以通过0H伸缩振动模的振动谱得到直接证实。     

Vibrational recognition of hydrogen-bonded water networks on a metal surface

The adsorption of water on Pt(111) surface has been studied with ab initio molecular dynamics simulation. Both the energetics and vibrational dynamics indicate the existence of a well-ordered molecular bilayer on this surface. This conclusion is in contrast to the recent result of water on Ru(0001) surface, but agrees with available experiments. In addition, our calculation identifies two different hydrogen bonds in the bilayer. Both can be directly recognized from the vibrational spectra of the OH stretch modes.     

A continuum model for dephasing in mesoscopic systems

A model of continuous dephasing for one-dimensional mesoscopic conductors is proposed. The model is based on Büttiker's fictitious-probe model which is extended by attaching an infinite number of probes uniformly to various points on the conductor. The associated scattering problem is then solved. When the continuum limit is taken, it becomes possible to describe the dephasing as taking place everywhere. The dephasing rate enters into the model as an adjustable parameter. The effect of dephasing on the conductance for a double-barrier system is also studied numerically.     

Theory of superionic conduction in hydrogen-bonded systems

Among superionic conduction phenomena in various ionic materials, the conduction phenomenon associated with the motion of protons in hydrogen-bonded systems has aroused considerable interests with regard to a problem of whether the proton motion should be treated quantum mechanically or classically. In this paper we first describe a quantum mechanical mechanism of proton-induced ionic conduction in the superionic phase in zero-dimensional hydrogen-bonded M₃H(XO₄)₂[M = K, Rb, Cs, X = S,Se] materials, by giving a brief review on the theory developed by Ito and Kamimura. Then we discuss the characteristic difference between quantum mechanical and clasiical mechanisms in the case of proton-induced superionic condcuction, in paticular, by comparing characteristic time scales in quantum mechanical and classical diffusions in hydrogen-bonded systems. Finally a prediction is made on an anomalous behavior of terahertz spectra for Rb₃H(SeO₄)₂.     

Vibrational response of hydrogen-bonded interfacial water is dominated by intramolecular coupling

Using the surface-specific vibrational technique of vibrational sum-frequency generation, we reveal that the double-peaked structure in the vibrational spectrum of hydrogen-bonded interfacial water molecules originates from vibrational coupling between the stretch and bending overtone, rather than from structural effects. This is demonstrated by isotopic dilution experiments, which reveal a smooth transition from two peaks to one peak, as D2O is converted into HDO. Our results show that the water interface is structurally more homogeneous than previously thought.     

Vibrational dephasing in highly compressed liquid nitrogen studied with time-resolved stimulated raman gain spectroscopy

Abstract

In liquid nitrogen at 295 K we observe for the first time the minimum in the variation of the vibrational dephasing rate T^?1 ₂ with density at ρ = 2.15 × 10²². cm^?3. At higher densities the dephasing rate shows a steep rise with density. The observed behaviour shows good agreement with results of previously published molecular dynamics simulations.     

Scaling of the low-temperature dephasing rate in Kondo systems

We present phase coherence time measurements in quasi-one-dimensional Ag wires doped with Fe Kondo impurities of different concentrations n_{s}. Because of the relatively high Kondo temperature T_{K} approximately 4.3 K of this system, we are able to explore a temperature range from above T_{K} down to below 0.01T_{K}. We show that the magnetic contribution to the dephasing rate gamma_{m} per impurity is described by a single, universal curve when plotted as a function of T/T_{K}. For T>0.1T_{K}, the dephasing rate is remarkably well described by recent numerical results for spin S=1/2 impurities. At lower temperature, we observe deviations from this theory. Based on a comparison with theoretical calculations for S>1/2, we discuss possible explanations for the observed deviations.     

Correlation dynamics of qubit-qutrit systems in a classical dephasing environment

We study the time evolution of classical and quantum correlations for hybrid qubit-qutrit systems in independent and common dephasing environments. Our discussion involves a comparative analysis of the Markovian dynamics of negativity, quantum discord, geometric measure of quantum discord and classical correlation. For the case of independent environments, we have demonstrated the phenomenon of sudden transition between classical and quantum decoherence for qubit-qutrit states. In the common environment case, we have shown that dynamics of quantum and geometric discords might be completely independent of each other for a certain time interval, although they tend to be eventually in accord.     

Vibrational resonance in excitable neuronal systems

In this paper, we investigate the effect of a high-frequency driving on the dynamical response of excitable neuronal systems to a subthreshold low-frequency signal by numerical simulation. We demonstrate the occurrence of vibrational resonance in spatially extended neuronal networks. Different network topologies from single small-world networks to modular networks of small-world subnetworks are considered. It is shown that an optimal amplitude of high-frequency driving enhances the response of neuron populations to a low-frequency signal. This effect of vibrational resonance of neuronal systems depends extensively on the network structure and parameters, such as the coupling strength between neurons, network size, and rewiring probability of single small-world networks, as well as the number of links between different subnetworks and the number of subnetworks in the modular networks. All these parameters play a key role in determining the ability of the network to enhance the outreach of the localized subthreshold low-frequency signal. Considering that two-frequency signals are ubiquity in brain dynamics, we expect the presented results could have important implications for the weak signal detection and information propagation across neuronal systems.     

Vibrational properties of hierarchical systems

The vibrational properties of one-dimensional hierarchical systems are investigated and results are obtained for both their eigenvalues and eigenvectors. Two cases are considered, the first one with a hierarchy of spring constants and the latter with a hierarchy in the masses. In both cases the eigenspectrum is found to be a zero-measure, two-scale Cantor set with a fractal dimension between 0 and 1. The scaling properties of the spectra are calculated using renormalization group techniques and are verified by extensive numerical work. The low-frequency density of states and low-temperature specific heat are calculated and a singularity is found in the scaling behavior. The eigenvectors are found to be either extended or critical and self-similar. A transfer matrix formalism is introduced to calculate the scaling properties of the envelope of the critical eigenvectors. Furthermore, a connection is established between the hierarchical vibration and diffusion problems, as well as to the same problems in random systems, thus showing the universality of the observed features.