Escape over a sharp-edged barrier: The theory of activation for the double oscillator

The noise-activated rate of escape over a sharp-edged potential barrier is obtained using Rayleigh's quotient for the pertinent eigenvalue of Kramers' Fokker-Planck model.     

Quantum tunneling at zero temperature in the strong friction regime

In the large damping limit we derive a Fokker-Planck equation in configuration space (the so-called Smoluchowski equation) describing a Brownian particle immersed into a thermal environment and subjected to a nonlinear external force. We quantize this stochastic system and survey the problem of escape over a double-well potential barrier. Our finding is that the quantum Kramers rate does not depend on the friction coefficient at low temperatures; i.e., we predict a superfluidity phenomenon in overdamped open systems. Moreover, at zero temperature we show that the quantum escape rate does not vanish in the strong friction regime. This result, therefore, is in contrast with the work by Ankerhold et al. [Phys. Rev. Lett. 87, 086802 (2001)]] in which no quantum tunneling is predicted at zero temperature.     

Phase escape of current-biased Josephson junctions

Switching current distributions of an Nb/Al--AlO_x/Nb Josephson junction are measured in a temperature range from 25~mK to 800~mK. We analyse the phase escape properties by using the theory of Larkin and Ovchinnikov (LO) which takes discrete energy levels into account. Our results show that the phase escape can be well described by the LO approach for temperatures near and below the crossover from thermal activation to macroscopic quantum tunneling. These results are helpful for further study of macroscopic quantum phenomena in Josephson junctions where discrete energy levels need to be considered.     

Tunneling as a Classical Escape Rate Induced by the Vacuum Zero-point Radiation

We make a brief review of the Kramers escape rate theory for the probabilistic motion of a particle in a potential well U(x), and under the influence of classical fluctuation forces. The Kramers theory is extended in order to take into account the action of the thermal and zero-point random electromagnetic fields on a charged particle. The result is physically relevant because we get a non-null escape rate over the potential barrier at low temperatures (T → 0). It is found that, even if the mean energy is much smaller than the barrier height, the classical particle can escape from the potential well due to the action of the zero-point fluctuating fields. These stochastic effects can be used to give a classical interpretation to some quantum tunneling phenomena. Relevant experimental data are used to illustrate the theoretical results.     

Hiding Information in Theories Beyond Quantum Mechanics,and It’s Application to the Black Hole Information Problem

The black hole information problem provides important clues for trying to piece together a quantum theory of gravity. Discussions on this topic have generally assumed that in a consistent theory of gravity and quantum mechanics, quantum theory is unmodified. In this review, we discuss the black hole information problem in the context of generalisations of quantum theory. In this preliminary exploration, we examine black holes in the setting of generalised probabilistic theories, in which quantum theory and classical probability theory are special cases. We are able to calculate the time it takes information to escape a black hole, assuming that information is preserved. In quantum mechanics, information should escape pure state black holes after half the Hawking photons have been emitted, but we find that this get’s modified in generalisations of quantum mechanics. Likewise the black-hole mirror result of Hayden and Preskill, that information from entangled black holes can escape quickly, also get’s modified. We find that although information exits the black hole as predicted by quantum theory, it is fairly generic that it fails to appear outside the black hole at this point—something impossible in quantum theory due to the no-hiding theorem. The information is neither inside the black hole, nor outside it, but is delocalised.     

Haldane-like antiferromagnetic spin chain in the large anisotropy limit

We consider the one dimensional, periodic spin chain with N sites, similar to the one studied by Haldane [1], however in the opposite limit of very large anisotropy and small nearest neighbour, anti-ferromagnetic exchange coupling between the spins, which are of large magnitude s. For a chain with an even number of sites we show that actually the ground state is non-degenerate and given by a superposition of the two Neél states, due to quantum spin tunnelling. With an odd number of sites, the Neél state must necessarily contain a soliton. The position of the soliton is arbitrary thus the ground state is N-fold degenerate. This set of states reorganizes into a band. We show that this occurs at order 2s in perturbation theory. The ground state is non-degenerate for integer spin, but degenerate for half-odd integer spin as is required by Kramers' theorem [18].     

Crystal field theory and the Shubnikov point groups

Two pieces of theory which have so far remained unconnected, crystal field theory and the theory of corepresentations of non-unitary groups, are brought together here for the study of the splitting of atomic energy levels in a crystalline field with the symmetry of one of the magnetic (Shubnikov) point groups. The cases of the various possible relative strengths of the crystalline field and of spin-orbit coupling are considered.

Tables are presented which enable the splitting of any atomic energy level to be obtained very easily in a crystalline field with the symmetry of any one of the 58 magnetic point groups. Examples of the use of these tables are given.

A discussion is given of the relevance of Kramers' theorem to the energy levels of electrons in surroundings with the symmetry of any one of the 58 magnetic point groups.     

Adiabatic electron transfer in polar media

The rate of electron transfer in polar media is calculated in the framework of the transition state theory. It is shown that this theory is valid if k _B T > (hω₀/2π), where ω₀ is the frequency of a particle motion at the barrier top. The pre-exponential factor of the rate constant is found to be dependent on the reaction heat, dielectric loss spectrum, ?(ω), and the nondiagonal matrix element, Г. The rate constant of charge transfer in water, with allowance for the resonance absorbtion region, is determined. The influence of the motion of the water complexes on the rate constant is considered and it is shown that the pre-exponential factor depends not only on the frequency of the complex vibrations, but also on its reorganization energy. The maximum value of the complex reorganization energy is calculated under the conditions where the theory is valid. In the particular case of the Debye dielectric loss spectrum the multidimensional activated complex theory is shown to be equivalent to the stochastic Alexandrov-Zusman's model and the Kramers' theory (the case of large viscosity). It is pointed out that the transition state theory allows the inertial degrees of freedom to be taken into account for a real dielectric loss spectrum, ?(ω).     

非绝热分子动力学的量子路径模拟

基于近期发展的经典-量子混合模拟非绝热分子动力学的量子路径方案,本文对5个典型势能面模型进行了模拟,包括单交叉模型、双交叉模型、拓展耦合模型、哑铃模型以及双弓模型.由于难以在严格意义上得到退相干速率,数值模拟中,我们比较了三个不同的退相干速率公式,包括冻结高斯波包近似退相干速率、能量分辨速率以及力分辨速率.在模拟过程中,我们恰当地处理了势能面跳跃时的能量守恒和力的反向问题.通过与全量子动力学模拟的精确结果进行对比发现,对于结构较简单的势能面模型,三种退相干速率都能得到较好的结果;然而对于较复杂的势能面模型,由于复杂量子干涉的原因,与其他混合经典-量子动力学方案类似,量子路径方案仍然难以得到较准确的结果.如何发展更加有效的混合经典-量子模拟方案,是未来研究的重要课题.     

Noise-activated escape from a sloshing potential well

We treat the noise-activated escape from a one-dimensional potential well of an overdamped particle, to which a periodic force of fixed frequency is applied. Near the well top, the relevant length scales and the boundary layer structure are determined. We show how behavior near the well top generalizes the behavior determined by Kramers, in the case without forcing. Our analysis includes the case when the forcing does not die away in the weak-noise limit. We discuss the relevance of scaling regimes, defined by the relative strengths of the forcing and the noise, to recent optical trap experiments.     

Explaining the Unobserved—Why Quantum Mechanics Ain’t Only About Information

A remarkable theorem by Clifton et al [Found Phys. 33(11), 1561–1591 (2003)] (CBH) characterizes quantum theory in terms of information-theoretic principles. According to Bub [Stud. Hist. Phil. Mod. Phys. 35 B, 241–266 (2004); Found. Phys. 35(4), 541–560 (2005)] the philosophical significance of the theorem is that quantum theory should be regarded as a “principle” theory about (quantum) information rather than a “constructive” theory about the dynamics of quantum systems. Here we criticize Bub’s principle approach arguing that if the mathematical formalism of quantum mechanics remains intact then there is no escape route from solving the measurement problem by constructive theories. We further propose a (Wigner-type) thought experiment that we argue demonstrates that quantum mechanics on the information-theoretic approach is incomplete.     

Nonequilibrium thermodynamics of nonisothermal activation: Escape over mesoscopic barriers: I. The stochastic process

It is argued that in noisy “macroscopic” systems (e.g. Josephson junctions) the effective potential for the pertinent degree of freedom (e.g. the magnetic flux) generally depends on the specimen's - local - temperature and, hence, that it should be given a thermodynamical (rather than the usual mechanical) significance. A Brownian motion theory of the ensuing nonequilibrium thermodynamics will be presented, which generalizes Kramers' model for thermal activation to include nonisothermal effects. Inter alia it is shown how in the steady state the thermodynamic fluctuation potential (the “availability”) arises as the natural generalization of either the Gibbs or the Helmholtz free energy.     

Energy relaxation and thermalization of hot electrons in quantum wires

We develop a theory of energy relaxation and thermalization of hot carriers in clean quantum wires. Our theory is based on a controlled perturbative approach for large excitation energies and emphasizes the important roles of the electron spin and finite temperature. Unlike in higher dimensions, relaxation in one-dimensional electron liquids requires three-body collisions and is much faster for particles than holes which relax at nonzero temperatures only. Moreover, comoving carriers thermalize more rapidly than counterpropagating carriers. Our results are quantitatively consistent with a recent experiment.     

Investigation of Noise-Induced Escape Rate: A Quantum Mechanical Approach

A quantum system coupled to a heat-bath in non-equilibrium environment is considered to study the problem of noise-induced escape rate from a metastable state in the moderate to strong friction limit (Kramers’ regime). It is known that starting from an initial coherent state representation of bath oscillators, one can derive a c-number generalized quantum Langevin equation where the quantum correction terms appear as a coupled infinite set of hierarchy of equations. For practical purpose, one should truncate these equations after a certain order. In our present development, we calculate the quantum correction terms in a closed analytical form based on a systematic perturbation technique and then derive the lowest order quantum correction factor exactly in the case of an Ohmic dissipative bath. Finally, to demonstrate its applicability, the effective equation of motions has been used to study the barrier crossing dynamics which incorporates the quantum correction factors.     

Rate coefficients and kinetic isotope effects of the abstraction reaction of H atoms from methylsilane

ABSTRACT

Thermal rate constants for chemical reactions using improved canonical variational transition state theory (ICVT) with small-curvature tunnelling (SCT) contributions in a temperature range 180–2000 K are reported. The general procedure is used with high-quality ab initio computations and semi-classical reaction probabilities along the minimum energy path (MEP). The approach is based on a vibrational adiabatic reaction path and is applied to the multiple-channel hydrogen abstraction reaction H + SiH₃CH₃ → products and its isotopically substituted variants. All the degrees of freedom are optimised and harmonic vibrational frequencies and zero-point energies are calculated at the MP2 level with the cc-pVTZ basis set. Single-point energies are calculated at a higher level of theory; CCSD(T)-F12a/VTZ-F12. ICVT/SCT rate constants show that the quantum tunnelling contributions at low temperatures are relatively important and the H-abstraction channel from SiH₃ group of SiH₃CH₃ is the major pathway. The total rate constants are given by the following expression: k_tot(ICVT/SCT) = 2.29 10^?18 T^2.42 exp(?350.9/T) cm³ molec^?1 s^?1. These calculated rates are in agreement with the available experiments. The ICVT/SCT method is further exploited to predict primary and secondary kinetic isotope effects, respectively).     

Femtosecond quantum dynamics of diatomic molecules in optically dense gaseous media

A consistent quantum theory of a two-pulse pump-probe experiment in the femto-and picosecond spectroscopy of diatomic molecules is developed. The theory aims at the use of weak quantum femtosecond light pulses to excite molecular coherence. It is suggested that the experiment be realized using a double-frequency excitation scheme that is feasible for Na₂ molecules. On the basis of the theory developed, the luminescence signals are calculated at different temperatures and different optical densities of the medium for the time range from 100 fs to ~ 100 ps. The results obtained show the presence of a strong dependence of the time and frequency spectra of a luminescence signal on the optical density of the medium at temperatures from 50 to 300 K. The proposed approach makes it possible to use the quantum coherence properties of optically dense media for more detailed study of the vibronic dynamics of diatomic molecules, in particular, detection of weak optical transitions.     

国债远期利率的量子场理论模型构建

随着我国利率市场化改革的全面推进和利率衍生品数量的增加,如何对远期利率进行精确与合理建模,就显得十分重要和紧迫.本文利用金融物理学中可有效纳入日历时间和到期时间两个维度上的国债远期利率之间不完全相关性的量子场论方法,对2011年1月4日到2016年12月30日的国债瞬时远期利率的实际市场演化进行建模,并将其结果与传统金融只能考虑日历时间方向上的相关性的主流两因子Heath-Jarrow-Morton (HJM)模型的实证结果进行比较.研究结果表明,考虑心理感知剩余时间变量后的量子场理论模型,提供了对实际的国债远期利率的92.67%的拟合优度,优于经典的最优两因子HJM模型69.02%的拟合精度.此外,分别将估计所得的最优参数代入最优量子场理论模型和两因子HJM模型下的远期利率更新方程,对2017年1月3日到2017年12月30日的100个期限的瞬时远期利率的250个瞬时远期利率的期限结构进行回测检验,从平均瞬时远期利率、均方根误差和Theil不等系数三个方面的结果均显示出量子场理论模型对国债远期利率建模的优越性.这些结果对将量子场理论引入到以国债为标的各种金融产品的定价和相关的利率风险管理、银行和金融公司的量化分析以及固定收益证券领域的实践者们均具有重要意义.     

Reaction rate theory: what it was, where is it today, and where is it going?

A brief history is presented, outlining the development of rate theory during the past century. Starting from Arrhenius [Z. Phys. Chem. 4, 226 (1889)], we follow especially the formulation of transition state theory by Wigner [Z. Phys. Chem. Abt. B 19, 203 (1932)] and Eyring [J. Chem. Phys. 3, 107 (1935)]. Transition state theory (TST) made it possible to obtain quick estimates for reaction rates for a broad variety of processes even during the days when sophisticated computers were not available. Arrhenius' suggestion that a transition state exists which is intermediate between reactants and products was central to the development of rate theory. Although Wigner gave an abstract definition of the transition state as a surface of minimal unidirectional flux, it took almost half of a century until the transition state was precisely defined by Pechukas [Dynamics of Molecular Collisions B, edited by W. H. Miller (Plenum, New York, 1976)], but even this only in the realm of classical mechanics. Eyring, considered by many to be the father of TST, never resolved the question as to the definition of the activation energy for which Arrhenius became famous. In 1978, Chandler [J. Chem. Phys. 68, 2959 (1978)] finally showed that especially when considering condensed phases, the activation energy is a free energy, it is the barrier height in the potential of mean force felt by the reacting system. Parallel to the development of rate theory in the chemistry community, Kramers published in 1940 [Physica (Amsterdam) 7, 284 (1940)] a seminal paper on the relation between Einstein's theory of Brownian motion [Einstein, Ann. Phys. 17, 549 (1905)] and rate theory. Kramers' paper provided a solution for the effect of friction on reaction rates but left us also with some challenges. He could not derive a uniform expression for the rate, valid for all values of the friction coefficient, known as the Kramers turnover problem. He also did not establish the connection between his approach and the TST developed by the chemistry community. For many years, Kramers' theory was considered as providing a dynamic correction to the thermodynamic TST. Both of these questions were resolved in the 1980s when Pollak [J. Chem. Phys. 85, 865 (1986)] showed that Kramers' expression in the moderate to strong friction regime could be derived from TST, provided that the bath, which is the source of the friction, is handled at the same level as the system which is observed. This then led to the Mel'nikov-Pollak-Grabert-Hanggi [Mel'nikov and Meshkov, J. Chem. Phys. 85, 1018 (1986); Pollak, Grabert, and Hanggi, ibid. 91, 4073 (1989)] solution of the turnover problem posed by Kramers. Although classical rate theory reached a high level of maturity, its quantum analog leaves the theorist with serious challenges to this very day. As noted by Wigner [Trans. Faraday Soc. 34, 29 (1938)], TST is an inherently classical theory. A definite quantum TST has not been formulated to date although some very useful approximate quantum rate theories have been invented. The successes and challenges facing quantum rate theory are outlined. An open problem which is being investigated intensively is rate theory away from equilibrium. TST is no longer valid and cannot even serve as a conceptual guide for understanding the critical factors which determine rates away from equilibrium. The nonequilibrium quantum theory is even less well developed than the classical, and suffers from the fact that even today, we do not know how to solve the real time quantum dynamics for systems with "many" degrees of freedom.