Semi-Empirical Model to Retrieve Finite Temperature Terahertz Absorption Spectra using Morse Potential

Terahertz (THz) absorption is a fingerprint property of materials, due to the underlying low-frequency vibration/phonon modes being strongly dependent on the chemical constitutions and microscopic structures. The low excitation energies (0.414-41.4 meV) are related to two intrinsic properties of THz vibrations: the potential energy surfaces (PESs) are shallow, and the vibrationally excited states are usually populated via thermal fluctuations. The shallow PESs make the vibrations usually anharmonic, leading to redshifted vibrational excited state absorption; combined with considerable vibrational excited states population, characteristic THz signals are usually redshifted and congested with varying degrees at different temperatures. Combining existing experimental THz spectra at low temperatures, first principles vibration analysis, and the Morse potential, we developed a semi-empirical model to evaluate the anharmonicity of the low-frequency modes. The model was benchmarked with purine molecular crystal to generate THz spectra at different temperatures, the results were consistent with experiments. The good agreement suggests this model would facilitate the application of THz spectroscopy in molecular crystal characterization.     

Geometric analysis of anharmonic downward distortion following paths

A mathematical aspect of the anharmonic downward distortion following (ADDF) path is discussed. The ADDF method is utilized as an automated reaction path search method, which can explore transition state geometries on a potential energy surface from a potential minimum. We show that the maximum number of the ADD stationary paths intersecting the potential minimum is 2^{f + 1} ? 2 , where f denotes the degree of freedom of the system. We also show that the bifurcation of the ADD stationary path is essential to detect all the transition states connected from a given minimum. The ADDF computation is demonstrated for a H₂O molecule in which pitchfork bifurcation is observed.     

Anharmonic Effect of the Unimolecular Isomerization/Decomposition of Benzyne

The anharmonic and harmonic rate constants were calculated for the unimolecular decomposition of o‐benzyne, the isomerization of o‐benzyne to m‐benzyne, the isomerization of m‐benzyne to p‐benzyne and unimolecular decomposition of p‐benzyne by using the Rice–Ramsperger–Kassel–Marcus (RRKM) theory respectively, in the canonical and microcanonical systems. The geometry and the vibrational frequencies were calculated by MP2 and B3LYP methods with 6‐311G(d,p) basis set and the barrier energies were corrected using CBS‐QB3 theory. The anharmonic effect on the reactions was also examined. Comparison of results for the decompositions of benzyne indicate that both in microcanonical and canonical cases, the anharmonic effect on the decomposition of the o‐C₆H₄ and p‐C₆H₄ are significant, while the anharmonic effect on the two isomerizations are not pronounced.     

参数激励耦合系统的复杂动力学行为分析

分析了耦合van der Pol振子参数共振条件下的复杂动力学行为．基于平均方程，得到了参数平面上的转迁集，这些转迁集将参数平面划分为不同的区域，在各个不同的区域对应于系统不同的解．随着参数的变化，从平衡点分岔出两类不同的周期解，根据不同的分岔特性，这两类周期解失稳后，将产生概周期解或3—D环面解，它们都会随参数的变化进一步导致混吨．发现在系统的混沌区域中，其混吨吸引子随参数的变化会突然发生变化，分解为两个对称的混吨吸引子．值得注意的是，系统首先是由于2—D环面解破裂产生混吨，该混吨吸引子破裂后演变为新的混吨吸引子，却由倒倍周期分岔走向3—D环面解，也即存在两条通向混沌的道路：倍周期分岔和环面破裂，而这两种道路产生的混吨吸引子在一定参数条件下会相互转换．     

Direct Shocks in a Vibrationally Nonequilibrium Gas

Direct shocks in flows of a high-temperature diatomic gas with rotational and vibrational degrees of freedom are considered. Gas-dynamic parameters and populations of molecular vibrational levels behind a shock are studied for the case of disturbance of vibrational equilibrium in an incident flow.     

Periodic and Non-Periodic Oscillations of a Class of Hysteretic Two Degree of Freedom Systems

The equations governing the response of hysteretic systems to sinusoidal forces, which are memory dependent in the classical phase space, can be given as a vector field over a suitable phase space with increased dimension. Hence, the stationary response can be studied with the aids of classical tools of nonlinear dynamics, as for example the Poincaré map. The particular system studied in the paper, based on hysteretic Masing rules, allows the reduction of the dimension of the phase space and the implementation of efficient algorithms. The paper summarises results on one degree of freedom systems and concentrates on a two degree of freedom system as the prototype of many degree of freedom systems. This system has been chosen to be in 1:3 internal resonance situation. Depending on the energy dissipation of the elements restoring force, the response may be more or less complex. The periodic response, described by frequency response curves for various levels of excitation intensity, is highly complex. The coupling produces a strong modification of the response around the first mode resonance, whereas it is negligible around the second mode. Quasi-periodic motion starts bifurcating for sufficiently high values of the excitation intensity; windows of periodic motions are embedded in the dominion of the quasi-periodic motion, as consequence of a locking frequency phenomenon.     

Properties of Chaotic and Regular Boundary Crisis in Dissipative Driven Nonlinear Oscillators

The phenomenon of the chaotic boundary crisis and the related concept of the chaotic destroyer saddle has become recently a new problem in the studies of the destruction of chaotic attractors in nonlinear oscillators. As it is known, in the case of regular boundary crisis, the homoclinic bifurcation of the destroyer saddle defines the parameters of the annihilation of the chaotic attractor. In contrast, at the chaotic boundary crisis, the outset of the destroyer saddle which branches away from the chaotic attractor is tangled prior to the crisis. In our paper, the main point of interest is the problem of a relation, if any, between the homoclinic tangling of the destroyer saddle and the other properties of the system which may accompany the chaotic as well as the regular boundary crisis. In particular, the question if the phenomena of fractal basin boundary, indeterminate outcome, and a period of the destroyer saddle, are directly implied by the structure of the destroyer saddle invariant manifolds, is examined for some examples of the boundary crisis that occur in the mathematical models of the twin-well and the single-well potential nonlinear oscillators.     

Numerical analysis of free vibrations of a beam with oscillators

The problem of free vibrations of a beam with free ends of variable cross section and mass, from which point masses (oscillators) are suspended by bars, is considered. It is shown that parametric resonances can occur in this oscillating system. Numerical examples showing the efficiency of the calculation method proposed are given. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 47, No. 4, pp. 135–144, July–August, 2006.     

Transition to escape in a system of coupled oscillators

We study a Hamiltonian system of coupled oscillators derived from two forced pendulums, connected with a torsional spring. The uncoupled limit is described by two identical oscillators, each possessing a homoclinic orbit separating bounded from unbounded motion. We focus on intermediate energy levels which lead to detained motions, defined as trajectories that, though unbounded as t → ∞, oscillate within the region defined by the homoclinic orbit of the unperturbed system for a long but finite time. We analyze the existence and behavior of these motions in terms of equipotential surfaces. These curves provide bounds on the motion of the system and are shown to be closed for low energies. However, above some critical energy level the equipotential curves become open. The detained trajectories are shown to arise from the region of phase space that was, for appropriate energies, stochastic. These motions remain within this region for long times before finally “leaking out” of the opening in the equipotential curves and proceeding to infinity.     

Multi-frequency oscillations in self-excited systems

A self-excited three-mass chain system is considered here. For a self-excitation of van der Pol type, the possibility of multi-frequency oscillations is investigated. Both analytical approximate solutions and numerical simulation are used. The averaging method is used to establish existence and stability of the normal modes, the two-frequency modes as well as the three-frequency oscillations solutions. We found at first that the single mode seems to prevail. However a three-frequency solution can be stabilised by adapting the system slightly. A generic bifurcation diagram is given where all the possible phase portraits are sketched. The flow turns out to be quite predictable. There is no “room” for chaos or strange attractors. This behaviour is not typical for systems of coupled oscillators but turns out to be partly related to the involved symmetries as well as the particular choice of the system parameters.