Projections of quantum observables onto classical degrees of freedom in mixed quantum-classical simulations: understanding linear response failure for the photoexcited hydrated electron

We present a general analytic method for understanding how specific motions of a classical bath influence the dynamics of quantum-mechanical observables in mixed quantum-classical molecular dynamics simulations. We apply our method and develop expressions for the special case of quantum solvation, allowing us to examine how specific classical solvent motions couple to the equilibrium energy fluctuations and nonequilibrium energy relaxation of a quantum-mechanical solute. As a first application of our formalism, we investigate the motions of classical water underlying the equilibrium and nonequilibrium excited-state solvent response functions of the hydrated electron; the results allow us to explain why the linear response approximation fails for this system.     

Collective dynamics of an end-grafted polymer brush in solvents of varying quality

The dynamic structure of a chemically end-grafted polystyrene brush bathed in solvents of varying interactions was studied by evanescent wave dynamic light scattering. It reveals distinct behavior under good and poor solvent conditions. The cooperative diffusion is a generic feature of a good solvent environment, whereas a second slow relaxation mode appears in the theta solvent regime. Its characteristics resemble self-diffusion of clusters in a gel while weak concentration fluctuations in the polymer brush decay similarly to a semidilute polymer solution.     

Field Theory Approaches to Relativistic Hydrodynamics

Just as non-relativistic fluids, oftentimes we find relativistic fluids in situations where random fluctuations cannot be ignored, with thermal and turbulent fluctuations being the most relevant examples. Because of the theory’s inherent nonlinearity, fluctuations induce deep and complex changes in the dynamics of the system. The Martin–Siggia–Rose technique is a powerful tool that allows us to translate the original hydrodynamic problem into a quantum field theory one, thus taking advantage of the progress in the treatment of quantum fields out of equilibrium. To demonstrate this technique, we shall consider the thermal fluctuations of the spin two modes of a relativistic fluid, in a theory where hydrodynamics is derived by taking moments of the Boltzmann equation under the relaxation time approximation.     

MuSR技术在凝聚态物理中的应用

缪子自旋弛豫/旋转(MuSR)实验技术利用缪子的自旋,在原子尺度上研究样品内部磁场的静态分布和动态涨落。文章介绍MuSR实验技术在凝聚态物理中的应用,阐述了MuSR在磁性、超导材料中发现的独特信息,包括磁有序、内部磁场分布、具有特定频率范围的自旋涨落,以及在半导体材料中获得杂质的电子状态和位置。这些应用表明 MuSR 对于理解关联电子材料复杂的物理现象及其物理机制具有重要意义。     

Solvent fluctuations and viscosity-dependent rates of solution reactions in a regime indescribable by the transition state theory

An organic molecule isomerizes in viscous solvents when appropriate cavities are formed around it in the course of slow diffusive thermal fluctuations of solvent molecules. The isomerization occurs when fast twisting (vibrational) fluctuations around a bond get to have large amplitudes in such cavities. This situation can be described by the two-reaction-coordinate model of Sumi and Marcus originally proposed for electron transfer reactions. In fact, the rate constant derived from this model fits nicely to that observed for thermal Z→E isomerization of substituted azobenzenes and N-benzylideneanilines. The rate constant is influenced by slow speeds of diffusive motions of solvent molecules, whose relaxation time τ is usually proportional to the solvent viscosity η. It has a form of k = 1/(k_TST⁻¹+k_f⁻¹), where k_TST, independent of τ, represents the rate constant expected from the transition state theory (TST), while k_f ∝ τ⁻ with 0 < ≤ 1 represents the part controlled by solvent fluctuations. An analytic expression of for the isomerization reactions is given in terms of physical parameters underlying the reaction mechanism with cavity formation.

This rate-constant formula is a general one applicable widely also to other solution reactions, covering from the TST-validated regime for a small τ to the TST-invalidated one for a large τ. In the former, k approaches k_TST since k_f k_TST, while in the latter, k approaches k_f since k_f k_TST, becoming decreasing with a decrease in the typical speed (∝ τ⁻¹) of solvent fluctuations. The dependence of k ≈ k_f ∝ η⁻ in the non-TST regime has often been observed also in biological reactions such as enzymatic ones. In this case, it is not appropriate to say that reactions are controlled by slow speeds of solvent fluctuations, but we should rather say that enzymes utilize this situation, which has been called conformational gating, in the course of solvent-fluctuation-driven conformational fluctuations of proteins. It has important meanings in protein functions.     

Theory of slightly fluctuating ratchets

We consider a Brownian particle moving in a slightly fluctuating potential. Using the perturbation theory on small potential fluctuations, we derive a general analytical expression for the average particle velocity valid for both flashing and rocking ratchets with arbitrary, stochastic or deterministic, time dependence of potential energy fluctuations. The result is determined by the Green’s function for diffusion in the time-independent part of the potential and by the features of correlations in the fluctuating part of the potential. The generality of the result allows describing complex ratchet systems with competing characteristic times; these systems are exemplified by the model of a Brownian photomotor with relaxation processes of finite duration.     

Langevin dynamics deciphers the motility pattern of swimming parasites

The parasite African trypanosome swims in the bloodstream of mammals and causes the highly dangerous human sleeping sickness. Cell motility is essential for the parasite's survival within the mammalian host. We present an analysis of the random-walk pattern of a swimming trypanosome. From experimental time-autocorrelation functions for the direction of motion we identify two relaxation times that differ by an order of magnitude. They originate from the rapid deformations of the cell body and a slower rotational diffusion of the average swimming direction. Velocity fluctuations are athermal and increase for faster cells whose trajectories are also straighter. We demonstrate that such a complex dynamics is captured by two decoupled Langevin equations that decipher the complex trajectory pattern by referring it to the microscopic details of cell behavior.     

Stochastic generalization for a hyperbolic model of spinodal decomposition

A model for diffusion and phase separation which takes into account exponential relaxation of the solute diffusion flux and its fluctuations is developed. The model describes a system undergoing phase separation governed by a partial differential equation of hyperbolic type. The analysis is done for the evolution of patterns in spinodal decomposition for the system supercooled below critical temperature. Analytical results show that relaxation processes of the solute diffusion flux lead to the selection of patterns with different wavenumbers. Considering spatial-temporal correlations of the flux fluctuations, we have found that the temporal correlations promote selecting large-period patterns, whereas the corresponding spatial correlations accelerate such processes.     

玻璃化转变的分子串模型中分子串弛豫模式的计算机模拟

基于玻璃化转变的分子串模型的哈密顿量(Hamiltonian),提出了模拟分子串第一和第二弛豫模式的蒙特卡罗(Monte Carlo)模拟方案.模拟得出的第一和第二弛豫模式的弛豫时间,与分子串模型中分子串弛豫方程所预言的结果完全一致,即理论预期和模拟结果相互印证.这不仅说明了分子串模型的分子串弛豫方程、至少是第一和第二弛豫模式的理论预言的正确性,同时也表明了本文所提出的模拟方法的有效性,并进一步明晰了分子串中分子的随机涨落和跃迁运动的图像,也为三态甚至是多态的分子串弛豫动力学研究,以及对进一步模拟分子串之 关键词： 弛豫动力学 蒙特卡罗模拟 分子串     

Fluctuations of the relaxation time in one-dimensional systems

The direct interaction of electrons with impurity field is represented as interelectronic interaction of a special kind which is called “dissipative”. This type of interaction is responsible for relaxation process and generally leads to fluctuations of the relaxation time. The probability distribution function for the mean free time of electrons is found in the white-noise approximation for a one-dimensional conductor. It is shown that the dielectric response function can be obtained in this case by averaging relevant expression over the fluctuations of the relaxation time.     

Initial density fluctuations effects on the microphase separation in ramified polymer mixture

Our study focuses on the initial density fluctuations effects on microphase separation in ramified polymer mixture. For this purpose, we introduce a screening length κ   by considering the condition that the scattered intensity should not be changed by cross-linking. We recover that κ²∼C/(χ−χi)${\kappa }^2\sim C/(\chi -{\chi }_i)$, where C is the rigidity constant of the network and χ the Flory parameter. Three regimes versus the temperature of the mixture are discussed. The kinetics of the microphase separation is also studied through the relaxation rate. The derived relaxation rate evolution relative to ramified polymers mixture must be compared to that relative to a linear polymer mixture. Finally, we discuss the solvent effect on the microphase separation and we show that the initial fluctuations have little importance because of the excluded volume interaction.     

Non-linear spin fluctuations and phase transitions in itinerant electron magnets: CMR manganites

We present a review analyzing the effects of coupling of transverse magnons with longitudinal spin fluctuations in isotropic itinerant ferro- and antiferromagnets. It is shown that this coupling essentially changes the spectrum of longitudinal fluctuations. At low-temperatures their spectrum is dominated by the linear Landau relaxation, is purely quasielastic and described by a broad central peak of a paramagnon type. On approaching the critical temperature non-linear magnetic relaxation due to mode–mode couplings can dominate and lead to a rapid increase of the central peak and to a new mechanism of magnetic phase transitions governed by non-linear spin fluctuations. The formalism is applied to the CMR manganites where the observed quasielastic fluctuations can be viewed as non-linear spin-lattice fluctuations strongly affected by magnons.     

NMR STRUCTURAL INVESTIGATION OF THE BIOTIN-AVIDIN COMPLEX: A 13C NMR PARAMAGNETIC RELAXATION STUDY

The paramagnetic contributions to the spin-lattice relaxation rates of biotin ¹³C nuclei, induced by the presence in the water/DMSO solution of the TEMPOL nitroxide, have been analysed in the interaction with avidin. The paramagnetic relaxation data, obtained at different temperatures, indicate that the average solvent/spin-label exposure of biotin carbons is consistent with the conformational features previously observed for the complex in the crystal. The analysis of the paramagnetic perturbation profiles, derived from ¹³C spin lattice relaxation measurements, seems to be highly informative of the sterical aspects of interaction processes of large biopolymers with their ligands.     

Anisotropic spin fluctuations and superconductivity in "115" heavy fermion compounds: ⁵⁹Co NMR study in PuCoGa₅

We report results of ??Co nuclear magnetic resonance measurements on a single crystal of superconducting PuCoGa? in its normal state. The nuclear spin-lattice relaxation rates and the Knight shifts as a function of temperature reveal an anisotropy of spin fluctuations with finite wave vector q. By comparison with the isostructural members, we conclude that antiferromagnetic XY-type anisotropy of spin fluctuations plays an important role in mediating superconductivity in these heavy fermion materials.     

Nonequilibrium fluctuations of a thin metal diffuse film exposed to microwave radiation

Nonlinear fluctuations of the electron energy distribution function in a microwave-irradiated thin diffuse metal film are calculated in the nonlinear approximation for various energy relaxation models. The spectral density of the resulting nonequilibrium fluctuations is calculated as a function of the microwave-radiation power for various ratios between the electron-phonon and electron-electron relaxation rates.     

Energy dependence of quasiparticle relaxation in a disordered fermi liquid

A spectroscopic method is applied to measure the inelastic quasiparticle relaxation rate in a disordered Fermi liquid. The quasiparticle relaxation rate gamma is deduced from the magnitude of fluctuations in the local density of states, which are probed using resonant tunneling through a localized impurity state. We study its dependence on the excitation energy E measured from the Fermi level. In a disordered metal (heavily doped GaAs) we find that gamma~E3/2 within the experimentally accessible energy interval, in agreement with the Altshuler-Aronov theory for electron-electron interactions in diffusive conductors.     

Dynamical properties of an asymmetric bistable system with quantum fluctuations in the strong-friction limit

The dynamical properties of an overdamped Brownian particle moving in an asymmetric bistable system with quantum fluctuations are investigated. Within the strong-friction limit (the quantum Smoluchowski regime), the analytic expression for the relaxation time of the system is derived by means of the projection-operator method, in which the effects of the memory kernels are taken into account. Based on the relaxation time, we consider both the overdamped quantum case and its classical counterpart.In these contexts, the effects of the quantum fluctuations and the asymmetry of the potential are discussed. It is found that: (i) The quantum effects in an asymmetric bistable system on time scales of the relaxation process are more prominent for lower temperatures and smaller asymmetries of the potential. (ii) The quantum effects speed up the rate of fluctuation decay of the state-space variable for lower temperatures. (iii) The asymmetry of the potential first slows down the rate of fluctuation decay of the state-space variable and then increases it.     

Continuum Model for Electronic Polarization Based on a Novel Dielectric Response Function

基于连续介质模型推导了一个普适的描述电介质介电弛豫过程的响应函数. 该介电响应函数依赖于电介质的介电谱. 基于该函数推导得到了以前特殊情况下用于描述溶剂弛豫的响应函数一致的表达式.结合三种典型极性溶剂,水、甲醇和乙腈的介电谱,研究了三种溶剂在外加电场线性变化时的电子极化过程. 结果表明,溶剂的电子极化伴随着电子跃迁同步发生,没有时滞.     

Dielectric spectroscopy on aqueous solutions of some zwitterionic amino acids

The complex (electric) permittivity of aqueous solutions of dipolar solutes has been measured as a function of frequency between 1 MHz and 40 GHz. Solutes are the isomers DL-2-aminobutyric acid, DL-3-aminobutyric acid, and 4-aminobutyric acid, and also 6-aminohexanoic acid. The measured dielectric spectra show two dispersion/dielectric loss regions, one due to the orientational diffusion of the solute molecules the other one due to the dielectric relaxation of the solvent water. A relaxation spectral function based on a model of the solutions has been fitted to the measured frequency dependence of the complex permittivity. The values for the electric dipole moment and reorientation time of the zwitterionic part of the solute particles derived by this analysis from the measurements fairly agree with theoretical predictions. Quite remarkably, the dipole moment in solution of 4-aminobutyric acid and 6-aminohexanoic acid up to remarkably high solute concentrations is nearly constant. A noteworthy result for the hydration water of the amino acids is, that its relaxation time is almost independent of the solute dipole moment.