Classical Subsystem Research Articles

On the foundations of quantum physics

Some aspects of the interpretation of microscopic physics in terms of quantum theory are discussed. It is first emphasized that quantum theory is formulated in a Cartesian coordinate system; in other coordinates the result obtained with the help of the Hamiltonian formalism and commutation relations between ''canonically conjugated'' coordinate and momentum operators leads to a wrong version of quantum mechanics. In this connection the Feynman integral formalism is also discussed. In this formalism the measure is not well defined, and there is no idea how to distinguish between the true version of quantum mechanics and an incorrect one. In this respect, the Feynman approach consists of a mnemonic rule to generate perturbation series from an undefined zero-order term. The origin of time in the quantum framework is then analyzed in detail and illustrated by the example of atomic collisions. It is shown that the time-dependent Schr ¨ odinger equation for the closed three-body (two nuclei + electron) system has no physical meaning because in the high-impact energy limit it transforms into an equation with two independent time-like variables; time naturally appears in the stationary Schr ¨ odinger equation as a result of extraction of a classical subsystem (two nuclei) from a closed three-body system. Finally, following the well-known Einstein-Rosen-Podolsky experiment and Bell's inequality, we reiterate that the wave function must be interpreted as an actual field of information, in a form as elementary as the usual material particles and electromagnetic fields. In fact, experimental measurements transfer this quantum information field into the classical world, which is directly discernable. In my conclusion, the relation between physical reality and its mathematical formulation is discussed. 2012 Physics Essays Publication. (DOI: 10.4006/0836-1398-25.1.27) R ´

Hybrid Quantum/Classical Simulations of the Vibrational Relaxation of the Amide I Mode of N-Methylacetamide in D2O Solution

Hybrid quantum/classical molecular dynamics (MD) is applied to simulate the vibrational relaxation (VR) of the amide I mode of deuterated N-methylacetamide (NMAD) in aqueous (D(2)O) solution. A novel version of the vibrational molecular dynamics with quantum transitions (MDQT) treatment is developed in which the amide I mode is treated quantum mechanically while the remaining degrees of freedom are treated classically. The instantaneous normal modes of the initially excited NMAD molecule (INM(0)) are used as internal coordinates since they provide a proper initial partition of the system in quantum and classical subsystems. The evolution in time of the energy stored in each individual normal mode is subsequently quantified using the hybrid quantum-classical instantaneous normal modes (INM(t)). The identities of both the INM(0)s and the INM(t)s are tracked using the equilibrium normal modes (ENMs) as templates. The results extracted from the hybrid MDQT simulations show that the quantum treatment of the amide I mode accelerates the whole VR process versus pure classical simulations and gives better agreement with experiments. The relaxation of the amide I mode is found to be essentially an intramolecular vibrational redistribution (IVR) process with little contribution from the solvent, in agreement with previous theoretical and experimental studies. Two well-defined relaxation mechanisms are identified. The faster one accounts for ≈40% of the total vibrational energy that flows through the NMAD molecule and involves the participation of the lowest frequency vibrations as short-life intermediate modes. The second and slower mechanism accounts for the remaining ≈60% of the energy released and is associated to the energy flow through specific mid-range and high-frequency modes.

Electrochemical transistor based on bridge tunneling contact containing two redox groups

The method of kinetic equations was used to show that a bridge tunneling contact containing two redox groups in the sequential configuration immersed into a solution of electrolyte at the room temperature features pronounced transistor properties at a given set of physical system parameters. Valence electrons of redox groups interact strongly with the classical phonon subsystem of the liquid medium. Debye screening of the electric field in the tunneling gap and Coulomb repulsion between electrons in different redox groups are taken into account. The case of nonadiabatic electron transfer both between redox groups and between electrodes and redox groups is considered in the limit of infinitely high Coulomb repulsion between electrons in a redox group. For sufficiently high absolute values of difference δ between unperturbed energy levels of redox groups, the system features voltammetric characteristics typical for a transistor. The amplification effect appears due to a strong dependence of tunneling current on overpotential. The emphasis is upon the peculiaritiespeculiarities of voltammetric characteristics in the case of asymmetric tunneling contacts.

Berry phase and Hannay’s angle in a quantum-classical hybrid system

Berry phase, which had been discovered for more than two decades, provides us a very deep insight on the geometric structure of quantum mechanics. Its classical counterpart--Hannay's angle is defined if closed curves of action variables return to the same curves in phase space after a time evolution. In this paper, we study the Berry phase and Hannay's angle in a quantum-classical hybrid system under the Born-Oppenheimer approximation. By quantum-classical hybrid system, we denote a composite system consists of a quantum subsystem and a classical subsystem. The effects of subsystem-subsystem couplings on the Berry phase and Hannay's angle are explored. The results show that the Berry phase has been changed sharply by the couplings, whereas the couplings have small effect on the Hannay's angle.

Reverse Mathematics and Uniformity in Proofs without Excluded Middle

We show that when certain statements are provable in subsystems of constructive analysis using intuitionistic predicate calculus, related sequential statements are provable in weak classical subsystems. In particular, if a $\Pi^1_2$ sentence of a certain form is provable using E-HA${}^\omega$ along with the axiom of choice and an independence of premise principle, the sequential form of the statement is provable in the classical system RCA. We obtain this and similar results using applications of modified realizability and the Dialectica interpretation. These results allow us to use techniques of classical reverse mathematics to demonstrate the unprovability of several mathematical principles in subsystems of constructive analysis.

Dynamics of quantum-classical hybrid systems: Effect of matter-wave pressure

Radiation pressure affects the kinetics of a system exposed to the radiation and it constitutes the basis of laser cooling. In this paper, we study {\it matter-wave pressure} through examining the dynamics of a quantum-classical hybrid system. The quantum and classical subsystem have no explicit coupling to each other, but affect mutually via a changing boundary condition. Two systems, i.e., an atom and a Bose-Einstein condensate(BEC), are considered as the quantum subsystems, while an oscillating wall is taken as the classical subsystem. We show that the classical subsystem would experience a force proportional to $Q^{-3}$ from the quantum atom, whereas it acquires an additional force proportional to $Q^{-2}$ from the BEC due to the atom-atom interaction in the BEC. These forces can be understood as the {\it matter-wave pressure}.

Violation of multipartite Bell inequalities with classical subsystems via operationally local transformations

Recently, it was demonstrated by Son et al., Phys. Rev. Lett. 102, 110404 (2009), that a separable bipartite continuous-variable quantum system can violate the Clauser-Horne-Shimony-Holt (CHSH) inequality via operationally local transformations. Operationally local transformations are parametrized only by local variables; however, in order to allow violation of the CHSH inequality, a maximally entangled ancilla was necessary. The use of the entangled ancilla in this scheme caused the state under test to become dependent on the measurement choice one uses to calculate the CHSH inequality, thus violating one of the assumptions used in deriving a Bell inequality, namely, the free will or statistical independence assumption. The novelty in this scheme however is that the measurement settings can be external free parameters. In this paper, we generalize these operationally local transformations for multipartite Bell inequalities (with dichotomic observables) and provide necessary and sufficient conditions for violation within this scheme. Namely, a violation of a multipartite Bell inequality in this setting is contingent on whether an ancillary system admits any realistic local hidden variable model (i.e., whether the ancilla violates the given Bell inequality). These results indicate that violation of a Bell inequality performed on a system does not necessarily imply that the system is nonlocal. In fact, the system under test may be completely classical. However, nonlocality must have resided somewhere, this may have been in the environment, the physical variables used to manipulate the system or the detectors themselves provided the measurement settings are external free variables.

Decoherence and quantum-classical dynamics in a dissipative bath

The dynamics of a mixed quantum-classical system, in which the classical subsystem interacts with a dissipative bath, is investigated. This description of the dynamics will be appropriate if the details of the bath dynamics are unimportant but its presence plays an important role in the dissipation of energy to the environment. In this dynamical description, which can be simulated employing an ensemble of stochastic surface-hopping trajectories, the strength of the dissipation is controlled by a friction coefficient. We show that if decoherence, whose effects are controlled by the bath friction, is sufficiently rapid, the equation of motion can be reduced to a master equation. Thus, decoherence and the validity of master equation models may be explored as a function of bath friction. We use this framework to study the mechanism of decoherence in a simple model nonadiabatic chemical reaction.

A pseudobond parametrization for improved electrostatics in quantum mechanical/molecular mechanical simulations of enzymes

The pseudobond method is used in quantum mechanical/molecular mechanical (QM/MM) simulations in which a covalent bond connects the quantum mechanical and classical subsystems. In this method, the molecular mechanical boundary atom is replaced by a special quantum mechanical atom with one free valence that forms a bond with the rest of the quantum mechanical subsystem. This boundary atom is modified through the use of a parametrized effective core potential and basis set. The pseudobond is designed to reproduce the properties of the covalent bond that it has replaced, while invoking as small a perturbation as possible on the system. Following the work of Zhang [J. Chem. Phys. 122, 024114 (2005)], we have developed new pseudobond parameters for use in the simulation of enzymatic systems. Our parameters yield improved electrostatics and deprotonation energies, while at the same time maintaining accurate geometries. We provide parameters for C(ps)(sp(3))-C(sp(3)), C(ps)(sp(3))-C(sp(2),carbonyl), and C(ps)(sp(3))-N(sp(3)) pseudobonds, which allow the interface between the quantum mechanical and molecular mechanical subsystems to be constructed at either the C(alpha)-C(beta) bond of a given amino acid residue or along the peptide backbone. In addition, we demonstrate the efficiency of our parametrization method by generating residue-specific pseudobond parameters for a single amino acid. Such an approach may enable higher accuracy than general purpose parameters for specific QM/MM applications.

Effect of quantum subsystem–subsystem coupling in hybrid systems

In this paper, we study the effect of quantum subsystem–subsystem coupling on the magnetic-like field that the classical subsystem feels in a quantum–classical hybrid system. The hybrid system is composed of a classical magnetic particle and two coupled spins. We show that (i) when the spin–spin interaction is equal to the magnetic–spin interaction, the magnetic-like field changes sharply. This observation becomes more clear when the distance between the two subsystems is much longer than the magnetic particle's rotating radius. (ii) When the spin–spin interaction is larger than the coupling between the quantum classical systems, the effect that the quantum subsystem acts on in the classical part approaches zero. Some useful applications are also discussed.

Determination of rate constants for the uptake process involving SO 2 and an aerosol particle. A quantum mechanics/molecular mechanics and quantum statistical investigation

We present a combined quantum mechanics/molecular mechanics and quantum statistical investigation of the interactions between a molecule (SO 2) and an aerosol particle including rate constants for the uptake process. A coupled cluster/molecular mechanics method including explicit polarization is used along with a quantum statistical method for calculating sticking coefficients. The importance of the polarization of the classical subsystem (the aerosol particle), the size of the classical subsystem and the size of one-electron basis sets are studied. The interaction energy is divided into van der Waals, electrostatic and polarization contributions. Relevant binding sites for the evaluation of the sticking coefficient are identified. These are classified into three groups according to the strength of the molecule–aerosol particle interaction energy. The identification of binding sites provides relevant information used in the quantum statistical method and thereby knowledge of the magnitude of the sticking coefficients for the different binding sites along with the total rates for the uptake processes between the aerosol particle and the SO 2 molecule.

Variational principle for mixed classical–quantum systems

An extended variational principle providing the equations of motion for a system consisting of interacting classical, quasiclassical, and quantum components is presented, and applied to the model of bilinear coupling. The relevant dynamical variables are expressed in the form of a quantum state vector that includes the action of the classical subsystem in its phase factor. It is shown that the statistical ensemble of Brownian state vectors for a quantum particle in a classical thermal environment can be described by a density matrix evolving according to a nonlinear quantum Fokker–Planck equation. Exact solutions of this equation are obtained for a two-level system in the limit of high temperatures, considering both stationary and nonstationary initial states. A treatment of the common time shared by the quantum system and its classical environment as a collective variable, rather than as a parameter, is presented in the Appendix. PACS Nos.: 03.65.–w, 03.65.Sq, 05.30.–d, 45.10.Db

Generalization of Classical Mechanics for Nuclear Motions on Nonadiabatically Coupled Potential Energy Surfaces in Chemical Reactions

Classical trajectory study of nuclear motion on the Born-Oppenheimer potential energy surfaces is now one of the standard methods of chemical dynamics. In particular, this approach is inevitable in the studies of large molecular systems. However, as soon as more than a single potential energy surface is involved due to nonadiabatic coupling, such a naive application of classical mechanics loses its theoretical foundation. This is a classic and fundamental issue in the foundation of chemistry. To cope with this problem, we propose a generalization of classical mechanics that provides a path even in cases where multiple potential energy surfaces are involved in a single event and the Born-Oppenheimer approximation breaks down. This generalization is made by diagonalization of the matrix representation of nuclear forces in nonadiabatic dynamics, which is derived from a mixed quantum-classical representation of the electron-nucleus entangled Hamiltonian [Takatsuka, K. J. Chem. Phys. 2006, 124, 064111]. A manifestation of quantum fluctuation on a classical subsystem that directly contacts with a quantum subsystem is discussed. We also show that the Hamiltonian thus represented gives a theoretical foundation to examine the validity of the so-called semiclassical Ehrenfest theory (or mean-field theory) for electron quantum wavepacket dynamics, and indeed, it is pointed out that the electronic Hamiltonian to be used in this theory should be slightly modified.

Dissipation in a quantum-mechanical system

We consider a model of a dissipative quantum-mechanical system consisting of weakly coupled quantum and classical subsystems. The classical subsystem is assumed to be infinite, and thus serves as a means to transfer the energy of the quantum subsystem to the infinity (actually, to dissipate the energy). The quantum-classical coupling is treated in the spirit of the mean-field approximation. Solving the equations for the classical subsystem explicitly an effective dissipative Schrödinger equation for the quantum subsystem is obtained. The proposed method is illustrated by calculating the shape of the nonlinear resonance.

Effects of barrier fluctuation on the tunneling dynamics in the presence of classical chaos in a mixed quantum-classical system

We present a numerical investigation of the tunneling dynamics of a particle moving in a bistable potential with fluctuating barrier which is coupled to a non-integrable classical system and study the interplay between classical chaos and barrier fluctuation in the tunneling dynamics. We found that the coupling of the quantum system with the classical subsystem decreases the tunneling rate irrespective of whether the classical subsystem is regular or chaotic and also irrespective of the fact that whether the barrier fluctuates or not. Presence of classical chaos always enhances the tunneling rate constant. The effect of barrier fluctuation on the tunneling rate in a mixed quantum-classical system is to suppress the tunneling rate. In contrast to the case of regular subsystem, the suppression arising due to barrier fluctuation is more visible when the subsystem is chaotic.

Schrödinger-equation formalism for a dissipative quantum system

We consider a model dissipative quantum-mechanical system realized by coupling a quantum oscillator to a semi-infinite classical string which serves as a means of energy transfer from the oscillator to the infinity and thus plays the role of a dissipative element. The coupling between the two---quantum and classical---parts of the compound system is treated in the spirit of the mean-field approximation and justification of the validity of such an approach is given. The equations of motion of the classical subsystem are solved explicitly and an effective dissipative Schr\"odinger equation for the quantum subsystem is obtained. The proposed formalism is illustrated by its application to two basic problems: the decay of the quasistationary state and the calculation of the nonlinear resonance line shape.

The possibility of reconciling quantum mechanics with classical probability theory

We describe a scheme for constructing quantum mechanics in which a quantum system is considered as a collection of open classical subsystems. This allows using the formal classical logic and classical probability theory in quantum mechanics. Our approach nevertheless allows completely reproducing the standard mathematical formalism of quantum mechanics and identifying its applicability limits. We especially attend to the quantum state reduction problem.

General Approach to Quantum-Classical Hybrid Systems and Geometric Forces

We present a general theoretical framework for a hybrid system that is composed of a quantum subsystem and a classical subsystem. We approach such a system with a simple canonical transformation which is particularly effective when the quantum subsystem is dynamically much faster than the classical counterpart, which is commonly the case in hybrid systems. Moreover, this canonical transformation generates a vector potential which, on one hand, gives rise to the familiar Berry phase in the fast quantum dynamics and, on the other hand, yields a Lorentz-like geometric force in the slow classical dynamics.

Mean-field dynamics with stochastic decoherence (MF-SD): A new algorithm for nonadiabatic mixed quantum/classical molecular-dynamics simulations with nuclear-induced decoherence

The key factors that distinguish algorithms for nonadiabatic mixed quantum/classical (MQC) simulations from each other are how they incorporate quantum decoherence-the fact that classical nuclei must eventually cause a quantum superposition state to collapse into a pure state-and how they model the effects of decoherence on the quantum and classical subsystems. Most algorithms use distinct mechanisms for modeling nonadiabatic transitions between pure quantum basis states ("surface hops") and for calculating the loss of quantum-mechanical phase information (e.g., the decay of the off-diagonal elements of the density matrix). In our view, however, both processes should be unified in a single description of decoherence. In this paper, we start from the density matrix of the total system and use the frozen Gaussian approximation for the nuclear wave function to derive a nuclear-induced decoherence rate for the electronic degrees of freedom. We then use this decoherence rate as the basis for a new nonadiabatic MQC molecular-dynamics (MD) algorithm, which we call mean-field dynamics with stochastic decoherence (MF-SD). MF-SD begins by evolving the quantum subsystem according to the time-dependent Schrodinger equation, leading to mean-field dynamics. MF-SD then uses the nuclear-induced decoherence rate to determine stochastically at each time step whether the system remains in a coherent mixed state or decoheres. Once it is determined that the system should decohere, the quantum subsystem undergoes an instantaneous total wave-function collapse onto one of the adiabatic basis states and the classical velocities are adjusted to conserve energy. Thus, MF-SD combines surface hops and decoherence into a single idea: decoherence in MF-SD does not require the artificial introduction of reference states, auxiliary trajectories, or trajectory swarms, which also makes MF-SD much more computationally efficient than other nonadiabatic MQC MD algorithms. The unified definition of decoherence in MF-SD requires only a single ad hoc parameter, which is not adjustable but instead is determined by the spatial extent of the nonadiabatic coupling. We use MF-SD to solve a series of one-dimensional scattering problems and find that MF-SD is as quantitatively accurate as several existing nonadiabatic MQC MD algorithms and significantly more accurate for some problems.

Basis of Local Approach in Classical Statistical Mechanics

An ensemble of classical subsystems interacting with surrounding particles has been considered. In general case, a phase volume of the subsystems ensemble was shown to be a function of time. The evolutional equations of the ensemble are obtained as well as the simplest solution of these equations representing the quasi-local distribution with the temperature pattern being assigned. Unlike the Gibbs's distribution, the energy of interaction with surrounding particles appears in the distribution function, which make possible both evolution in the equilibrium case and fluctuations in the non-equilibrium one. The expression for local entropy is obtained. The derivation of hydrodynamic equations from Boltzmann equation has been analyzed. The hydrodynamic equations obtained from Boltzmann equation were shown to be equations for ideal liquid. Reasons for stochastic description in deterministic Hamilton's systems, conditions of applicability of Poincare's recurrence theorem as well as the problem of irreversibility have been considered.