On the Efficiency of Semiclassical and Classical Approximations of Quantum Fidelity in Many-Dimensional Systems

This thesis is focused on classical and semiclassical approximations of a specific quantum time correlation function, the “quantum fidelity.” Namely, we rigorously study the efficiency of a continuous class of algorithms for the evaluation of its classical limit and both the cost and the error of a particular semiclassical approximation of it. In the physics domain, quantum fidelity can be used to study the cross section of inelastic neutron scattering and phenomena like decoherence and irreversibility in NMR experiments. In chemical physics, quantum fidelity can be employed to compute the spectrum of a quantum state, to evaluate the accuracy of quantum dynamics on an approximate potential energy surface, and to verify the importance of nonadiabatic electronic transitions in molecules. Unfortunately, as for any numerical simulation of a quantum dynamical object, many-dimensional calculations of quantum fidelity are extremely expensive computationally. Classical methods, not including any quantum effect, are generally believed to be efficient approximations for the numerical evaluation of large systems’ properties when quantum effects are not important. We prove that, previous to this research, the computational costs of available algorithms for the simulation of classical fidelity increased exponentially with the number of degrees of freedom and we single out, within a continuous family of algorithms, the only one for which the number of trajectories needed for convergence is independent of the system’s dimensionality. Recently a semiclassical method, called “dephasing representation” (DR), has been proposed to approximate quantum fidelity accurately and efficiently. Although semiclassical methods, approximately including all types of quantum effects, are generally more accurate but much less efficient than classical methods, we prove that for the semiclassical DR there exists at least one algorithm for which the number of trajectories needed for convergence is independent of dimensionality and also that this semiclassical algorithm is even faster than the most efficient classical fidelity algorithm previously singled out. Encouraged by the surprising efficiency of the specific semiclassical method, we investigate the error of the DR compared to the quantum benchmark.

Adaptive Finite Element Methods for Multiscale Partial Differential Equations

Achim Nonnenmacher

Engineers rely on efficient simulations that provide them with reliable data in order to make proper engineering design decisions. The purpose of this thesis is to design adaptive numerical methods for multiscale problems in this spirit. We consider elliptic homogenization problems discretized by the finite element heterogeneous multiscale method (FE-HMM). Unlike standard (single-scale) finite element methods, our multiscale discretization scheme relies on coupled macro and micro finite elements. The framework of the HMM allows to design an algorithm that follows the classical finite element structure on the macro level. The fine scales of the multiscale problems are taken into account by replacing the element-wise numerical integration over unknown macroscopic data by a numerical integration over suitably averaged micro solutions. These micro solutions are obtained from micro FE problems on sampling domains within the macro elements. This thesis is divided into two parts. In the first part, we discuss a short and versatile FE implementation of the multiscale algorithm. The implementation is flexible, easy to use and to modify and can handle simplicial or quadrilateral FE and various macro-micro coupling conditions for the constrained micro problems. The implementation of time-dependent problems is also discussed. Numerical examples including three dimensional problems are presented and demonstrate the efficiency and the versatility of the computational strategy. In the second part (the main part of this thesis), we present an a posteriori error analysis for the FE-HMM. The a posteriori analysis enables us to estimate the accuracy of a numerical solution (and therefore its reliability) and further it allows for the design of adaptive numerical methods, which are the most efficient. The crucial component for the design of an adaptive multiscale method is the introduction of appropriate error indicators. As the error indicators depend on macroscopic data (such as the macroscopic diffusion tensor) that are not readily available, we construct error indicators that only depend on the available macro and micro FE solutions, available from previous computations. We provide a posteriori estimates for the upper and lower bound in the energy norm. The corresponding macroscopic mesh refinement strategy is therefore both reliable and efficient. The microscopic mesh is refined simultaneously and – under appropriate assumptions – optimally with the macroscopic mesh. This means that the strategy reduces the macro and micro error at the same rate. In the case of a uniformly oscillating tensor and exact micro computations, the standard a posteriori error estimates for the FEM applied to the homogenized problem are recovered. Numerical experiments confirm the efficiency and reliability of the adaptive multiscale method and demonstrate the optimality of the chosen macro-micro coupling. We extend the adaptive FE-HMM to higher order FE. We further derive a posteriori estimates for the error in quantities of interest that are needed to make certain design decisions; the quantity of interest is represented by a linear functional. We derive and analyze a multiscale counterpart to the classical dual-weighted residual method and design a corresponding goal-oriented adaptive multiscale method. The efficiency of the method is shown in numerical experiments.

EPFL2011

Beating the Efficiency of Both Quantum and Classical Simulations with a Semiclassical Method

Cesare Mollica, Jiri Vanicek

While rigorous quantum dynamical simulations of many-body systems are extremely difficult (or impossible) due to exponential scaling with dimensionality, the corresponding classical simulations ignore quantum effects. Semiclassical methods are generally more efficient but less accurate than quantum methods and more accurate but less efficient than classical methods. We find a remarkable exception to this rule by showing that a semiclassical method can be both more accurate and faster than a classical simulation. Specifically, we prove that for the semiclassical dephasing representation the number of trajectories needed to simulate quantum fidelity is independent of dimensionality and also that this semiclassical method is even faster than the most efficient corresponding classical algorithm. Analytical results are confirmed with simulations of fidelity in up to 100 dimensions with 21700-dimensional Hilbert space.

American Physical Society2011

Geometric Integrators for Nonadiabatic Molecular Quantum Dynamics Induced by the Interaction with the Electromagnetic Field

Aurélien Kevin Fabrice Patoz

Understanding the elementary steps involved in a chemical reaction forms the cornerstone of physical chemistry research. One way to deepen this understanding is by studying chemical and physical processes using linear and nonlinear spectroscopic techniques. However, the outcomes of such experiments can be difficult to decipher due to the interweaving of several effects. Therefore, in order to help experimentalists to disentangle such spectra, the role of theorists is to develop efficient tools that are able to accurately describe molecular systems. The starting point of such tools is solving the time-dependent Schrödinger equation. In this thesis, after implementing geometric integrators, which are based on a combination of the split-operator algorithm and Magnus expansion, for the exact nonadiabatic quantum dynamics of a molecule interacting with a time-dependent electromagnetic field, we derive and implement these geometric integrators for the time-dependent perturbation theory, the Condon, rotating-wave, and ultrashort-pulse approximations, as well as every possible combination thereof. As verified in several model systems, these integrators exactly preserve the geometric invariants, and achieve an arbitrary prescribed order of accuracy in the time step and an exponential convergence in the grid spacing. We also explore in more detail the ultrashort-pulse approximation and derive an analytical expression for the combination with the time-dependent perturbation theory; this expression significantly accelerates numerical calculations. We show that in the limit of the zero pulse width, the d-pulse approximation is recovered. We illustrate the performance of the introduced approximations, using a three-dimensional model of pyrazine, in which it is essential to go beyond the d-pulse limit in order to describe the dynamics correctly. The high-order algorithms are also applied to the photodissociation dynamics of iodomethane (CH3I), following its excitation to the A band. We implement a general split-operator with both discrete-variable and finite-basis representations that can treat one non-Cartesian, such as angular coordinate. To test the effect of various degrees of freedom and of the nonadiabatic dynamics, we apply these algorithms to one-, two-, and three-dimensional models of iodomethane, both in the presence and in the absence of nonadiabatic couplings. A full quantum calculation is, however, limited to problems with low dimensionality (approximately ten degrees of freedom). Beyond this, one must seek an affordable balance between computational efficiency and physical accuracy and can employ, for example, semiclassical methods that are based on classical trajectories. A simple semiclassical approximation that can treat larger systems and requires only local knowledge of the potential is the on-the-fly ab initio thawed Gaussian approximation. We implement a generalization of the method that goes beyond the Franck-Condon approximation and treats Herzberg-Teller active molecules. Our method is used to compute absorption spectra of phenyl radical and of benzene, for which the Herzberg-Teller contribution is essential.