We use an algebraic method to model the molecular collision dynamics of a collinear triatomic system. Beginning with a forced oscillator, we develop a mathematical framework upon which inelastic and reactive collisions are modeled. The model is considered algebraic because it takes advantage of the properties of a Lie algebra in the derivation of a time-evolution operator. The time-evolution operator is shown to generate both phase-space and quantum dynamics of a forced oscillator simultaneously. The model is considered semi-classical because only the molecule's internal degrees-of-freedom are quantized. The relative translation between the colliding atom and molecule in an exchange reaction (AB+C ->A+BC) contains no bound states and any possible tunneling is neglected so the relative translation is treated classically. The purpose of this dissertation is to develop a working model for the quantum dynamics of a collinear reactive collision. After a reliable model is developed we apply statistical mechanics principles by averaging collisions with molecules in a thermal bath. The initial Boltzmann distribution is of the oscillator energies. The relative velocities of the colliding particles is considered a thermal average. Results are shown of quantum transition probabilities around the transition state that are highly dynamic due to the coupling between the translational and transverse coordinate.
We use an algebraic method to model the molecular collision dynamics of a collinear triatomic system. Beginning with a forced oscillator, we develop a mathematical framework upon which inelastic and reactive collisions are modeled. The model is considered algebraic because it takes advantage of the properties of a Lie algebra in the derivation of a time-evolution operator. The time-evolution operator is shown to generate both phase-space and quantum dynamics of a forced oscillator simultaneously. The model is considered semi-classical because only the molecule's internal degrees-of-freedom are quantized. The relative translation between the colliding atom and molecule in an exchange reaction (AB+C ->A+BC) contains no bound states and any possible tunneling is neglected so the relative translation is treated classically. The purpose of this dissertation is to develop a working model for the quantum dynamics of a collinear reactive collision. After a reliable model is developed we apply statistical mechanics principles by averaging collisions with molecules in a thermal bath. The initial Boltzmann distribution is of the oscillator energies. The relative velocities of the colliding particles is considered a thermal average. Results are shown of quantum transition probabilities around the transition state that are highly dynamic due to the coupling between the translational and transverse coordinate.
Solving quantum dynamics is an exponentially difficult problem. Thus, an exact numerical solution is inaccessible for any condensed matter system.\nA promising approach is to divide the system into a quantum subsystem containing degrees of freedom which are of greater interest or those which have more profound quantum character (e.g., have smaller mass) and a classical bath containing the rest of the system.\nImposing such a partition and treating the bath classically results in quantum-classical dynamics. The quantum-classical Liouville equation is a general equation in the Hilbert space of quantum degrees of freedom while it resides in the phase space of the classical degrees of freedom.\nAny numerical solution to this equation requires representation of the quantum subsystem in some basis. Solutions to this equation have been already proposed in the subsystem, adiabatic and force bases, each with its own cons and pros.\n\nIn this work, the quantum-classical equations of motion are cast in the subsystem basis and subsequently mapped to a number of fictitious harmonic oscillators.\nThe result is quantum-classical dynamics in the mapping basis which treats both quantum and classical degrees of freedom on the same footing, i.e., in phase space. Neglecting a portion of the back reaction of the quantum-subsystem to classical bath results in an expression for the time evolution of an operator (density matrix) equal to its Poisson bracket with the Hamiltonian.\nThis equation can be solved in terms of characteristics to provide a computationally tractable method for calculating quantum-classical dynamical properties. The expressions for expectation values and correlation functions in this formalism are derived.\nCalculations on spin-boson system, barrier crossing models---the so called Tully models---and the Fenna-Mathews-Olson pigments show very good agreement between the results of this method and numerical solutions to the Schrödinger equation.
We study the time evolution of driven quantum systems using analytic, algebraic, and numerical methods. First, we obtain analytic solutions for driven free and oscillator systems by shifting the coordinate and phase of the undriven wave function. We also factorize the quantum evolution operator using the generators of the Lie algebra comprising the Hamiltonian. We obtain coupled ODE's for the time evolution of the Lie algebra parameters. These parameters allow us to find physical properties of oscillator dynamics. In particular we find phase-space trajectories and transition probabilities. We then search for chaotic behavior in the Lie algebra parameters as a signature for dynamical chaos in the quantum system. We plot the trajectories, transition probabilities, and Lyapunov exponents for a wide range of the following physical parameters: strength and duration of the driving force, frequency difference, and anharmonicity of the oscillator. We identify conditions for the appearance of chaos in the system.
A set of time-dependent basis states is obtained with a group of unitary transformations generated by a Lie algebra. Applying the time-dependent variational principle to the trial function subspace constructed from the linear combination of the time-dependent basis states gives rise to a set of ‘‘classical’’ equations of motion for the group parameters and the expansion coefficients from which the time evolution of the system state can be determined. The formulation is developed for a general Lie algebra as well as for the commonly encountered algebra containing homogeneous polynominal products of the coordinate Q and momentum P operators (or equivalently the boson creation a° and annihilation a operators) of order 0, 1, and 2. Explicit expressions for the transition amplitudes are derived by virtue of the cannonical transformation properties of the unitary transformation. The applicability of the present formalism in a variety of problems is implied by two illustrative examples: (a) a parametric amplifier; (b) the collinear collision of an atom with a Morse oscillator.
We study the back-reaction of quantum systems onto classical ones. Taking the starting point that semi-classical physics should be described at all times by a point in classical phase space and a quantum state in Hilbert space, we consider an unravelling approach, describing the system in terms of a classical-quantum trajectory. We derive the general form of the dynamics under the assumptions that the classical trajectories are continuous and the evolution is autonomous, and the requirement that the dynamics is linear and completely positive in the combined classical-quantum state. This requirement is necessary in order to consistently describe probabilities, and forces the dynamics to be stochastic when the back-reaction is non-zero. The resulting equations of motion are natural generalisations of the standard semi-classical equations of motion, but since the resulting dynamics is linear in the combined classical-quantum state, it does not lead to the pathologies which usually follow from evolution laws based on expectation values. In particular, the evolution laws we present account for correlations between the classical and quantum system, which resolves issues associated with other semi-classical approaches. In addition, despite a breakdown of predictability in the classical degrees of freedom, the quantum state evolves deterministically conditioned on the classical trajectory, provided a trade-off between decoherence and diffusion is saturated. As a result, the quantum state remains pure when conditioned on the classical trajectory. To illustrate these points, we numerically simulate a number of semi-classical toy models, including one of vacuum fluctuations as a source driving the expansion of the universe. Finally, we discuss the application of these results to semi-classical gravity, and the black-hole information problem.
The 1D collision between an atom and a diatomic molecule is investigated using an algebraic approach. Closed expressions for the quantum mechanical excitation transition probabilities are obtained. A Morse potential for the diatomic molecule is used. The classical trajectories are obtained in the united atom limit by taking an average over a finite number of states using the matrix density formalism, which allows the problem to be reformulated in terms of a time-dependent Hamiltonian. The system is studied in the interaction picture, which permits us to carry out an algebraic description through the approximation of the interaction potential in terms of a linear combination of the generators of the su (2) algebra. Comparisons with exact quantum mechanical results for transition probabilities in different systems are presented.
Many open quantum systems encountered in both natural and synthetic situations are embedded in classical-like baths. Often, the bath degrees of freedom may be represented in terms of canonically conjugate coordinates, but in some cases they may require a non-canonical or non-Hamiltonian representation. Herein, we review an approach to the dynamics and statistical mechanics of quantum subsystems embedded in either non-canonical or non-Hamiltonian classical-like baths which is based on operator-valued quasi-probability functions. These functions typically evolve through the action of quasi-Lie brackets and their associated Quantum-Classical Liouville Equations, or through quasi-Lie brackets augmented by dissipative terms. Quasi-Lie brackets possess the unique feature that, while conserving the energy (which the Noether theorem links to time-translation symmetry), they violate the time-translation symmetry of their algebra. This fact can be heuristically understood in terms of the dynamics of the open quantum subsystem. We then describe an example in which a quantum subsystem is embedded in a bath of classical spins, which are described by non-canonical coordinates. In this case, it has been shown that an off-diagonal open-bath geometric phase enters into the propagation of the quantum-classical dynamics. Next, we discuss how non-Hamiltonian dynamics may be employed to generate the constant-temperature evolution of phase space degrees of freedom coupled to the quantum subsystem. Constant-temperature dynamics may be generated by either a classical Langevin stochastic process or a Nosé–Hoover deterministic thermostat. These two approaches are not equivalent but have different advantages and drawbacks. In all cases, the calculation of the operator-valued quasi-probability function allows one to compute time-dependent statistical averages of observables. This may be accomplished in practice using a hybrid Molecular Dynamics/Monte Carlo algorithms, which we outline herein.