Coupled forward-backward trajectory approach for non-equilibrium electron-ion dynamics

We introduce a simple ansatz for the wavefunction of a many-body system based on coupled forward and backward-propagating semiclassical trajectories. This method is primarily aimed at, but not limited to, treating nonequilibrium dynamics in electron-phonon systems. The time-evolution of the system is obtained from the Euler-Lagrange variational principle, and we show that this ansatz yields Ehrenfest mean field theory in the limit that the forward and backward trajectories are orthogonal, and in the limit that they coalesce. We investigate accuracy and performance of this method by simulating electronic relaxation in the spin-boson model and the Holstein model. Although this method involves only pairs of semiclassical trajectories, it shows a substantial improvement over mean field theory, capturing quantum coherence of nuclear dynamics as well as electron-nuclear correlations. This improvement is particularly evident in nonadiabatic systems, where the accuracy of this coupled trajectory method extends well beyond the perturbative electron-phonon coupling regime. This approach thus provides an attractive route forward to the ab-initio description of relaxation processes, such as thermalization, in condensed phase systems

Improving the accuracy and efficiency of time-resolved electronic spectra calculations: Cellular dephasing representation with a prefactor

Time-resolved electronic spectra can be obtained as the Fourier transform of a special type of time correlation function known as fidelity amplitude, which, in turn, can be evaluated approximately and efficiently with the dephasing representation. Here we improve both the accuracy of this approximation---with an amplitude correction derived from the phase-space propagator---and its efficiency---with an improved cellular scheme employing inverse Weierstrass transform and optimal scaling of the cell size. We demonstrate the advantages of the new methodology by computing dispersed time-resolved stimulated emission spectra in the harmonic potential, pyrazine, and the NCO molecule. In contrast, we show that in strongly chaotic systems such as the quartic oscillator the original dephasing representation is more appropriate than either the cellular or prefactor-corrected methods.Comment: submitte

Capturing Vacuum Fluctuations and Photon Correlations in Cavity Quantum Electrodynamics with Multi-Trajectory Ehrenfest Dynamics

We describe vacuum fluctuations and photon-field correlations in interacting quantum mechanical light-matter systems, by generalizing the application of mixed quantum-classical dynamics techniques. We employ the multi-trajectory implementation of Ehrenfest mean field theory, traditionally developed for electron-nuclear problems, to simulate the spontaneous emission of radiation in a model quantum electrodynamical cavity-bound atomic system. We investigate the performance of this approach in capturing the dynamics of spontaneous emission from the perspective of both the atomic system and the cavity photon field, through a detailed comparison with exact benchmark quantum mechanical observables and correlation functions. By properly accounting for the quantum statistics of the vacuum field, while using mixed quantum-classical (mean field) trajectories to describe the evolution, we identify a surprisingly accurate and promising route towards describing quantum effects in realistic correlated light-matter systems

Mathematical Methods in Quantum Molecular Dynamics

This report summarizes the 2015 Oberwolfach meeting on mathematical methods in quantum molecular dynamics. Over decades this field has hosted considerable research activity from different disciplines, such as mathematics, chemistry, and physics. The workshop has aimed at bringing together these scientists for mutual benefit

On the Inversion of High Energy Proton

Inversion of the K-fold stochastic autoconvolution integral equation is an elementary nonlinear problem, yet there are no de facto methods to solve it with finite statistics. To fix this problem, we introduce a novel inverse algorithm based on a combination of minimization of relative entropy, the Fast Fourier Transform and a recursive version of Efron's bootstrap. This gives us power to obtain new perspectives on non-perturbative high energy QCD, such as probing the ab initio principles underlying the approximately negative binomial distributions of observed charged particle final state multiplicities, related to multiparton interactions, the fluctuating structure and profile of proton and diffraction. As a proof-of-concept, we apply the algorithm to ALICE proton-proton charged particle multiplicity measurements done at different center-of-mass energies and fiducial pseudorapidity intervals at the LHC, available on HEPData. A strong double peak structure emerges from the inversion, barely visible without it.Comment: 29 pages, 10 figures, v2: extended analysis (re-projection ratios, 2D

Parallel Implementation of Semiclassical Transition State Theory

This paper presents the parsctst code, an efficient parallel implementation of the semiclassical transition state theory (SCTST) for reaction rate constant calculations. Parsctst is developed starting from a previously presented approach for the computation of the vibrational density of states of fully coupled anharmonic molecules (Nguyen et al. Chem. Phys. Lett. 2010, 499, 915). The parallel implementation makes it practical to tackle reactions involving more than 100 fully coupled anharmonic vibrational degrees of freedom and also includes multidimensional tunneling effects. After describing the pseudocode and demonstrating its computational efficiency, we apply the new code for estimating the rate constant of the proton transfer isomerization reaction of the 2,4,6-tri-tert-butylphenyl to 3,5-di-tert-butylneophyl. Comparison with both theoretical and experimental results is presented. Parsctst code is user-friendly and provides a significant computational time saving compared to serial calculations. We believe that parsctst can boost the application of SCTST as an alternative to the basic transition state theory for accurate kinetics modeling not only in combustion or atmospheric chemistry, but also in organic synthesis, where bigger reactive systems are encountered

Development and application of semiclassical models for strong-field phenomena

Semiclassical models based on classical trajectories for the description of the electron motion in the continuum are a powerful tool of strong-field, ultrafast, and attosecond physics. The semiclassical models allow us to identify the specific mechanism of a phenomenon of interest and visualize it in terms of classical trajectories. Often these models are also computationally simple. In the present work we developed a range of new semiclassical models and applied them to various strong-field phenomena. Among these are: capture of electrons into Rydberg states, sequential multiple ionization, above-threshold ionization of the hydrogen molecule, multielectron effects due to the laser-induced polarization of the atomic ion, and strong-field holography with photoelectrons. We also used the semiclassical simulations to understand the results obtained using quantum optimal control theory, namely, optimization of the high-harmonic yield by shaping of the driving pulse. We developed a method capable of retrieving effective single-active electron potentials, which are required for semiclassical simulations. In this method the single-active electron potential is found as the result of an optimization procedure aimed at reproducing given photoelectron momentum distributions. Finally, we applied deep learning to retrieve the internuclear distance in a molecule ionized by a strong laser pulse from the photoelectron momentum distribution. The results of this thesis will serve as a basis for development of new generation of semiclassical models that are expected to combine accurate description of the ionization step, the ability to account for interference and multielectron effects, and numerical efficiency. The emergence of such models will open new perspectives in the theory of laser-matter interaction

Numerical computation of rare events via large deviation theory

An overview of rare events algorithms based on large deviation theory (LDT) is presented. It covers a range of numerical schemes to compute the large deviation minimizer in various setups, and discusses best practices, common pitfalls, and implementation trade-offs. Generalizations, extensions, and improvements of the minimum action methods are proposed. These algorithms are tested on example problems which illustrate several common difficulties which arise e.g. when the forcing is degenerate or multiplicative, or the systems are infinite-dimensional. Generalizations to processes driven by non-Gaussian noises or random initial data and parameters are also discussed, along with the connection between the LDT-based approach reviewed here and other methods, such as stochastic field theory and optimal control. Finally, the integration of this approach in importance sampling methods using e.g. genealogical algorithms is explored

Quantum Computing for Fusion Energy Science Applications

This is a review of recent research exploring and extending present-day quantum computing capabilities for fusion energy science applications. We begin with a brief tutorial on both ideal and open quantum dynamics, universal quantum computation, and quantum algorithms. Then, we explore the topic of using quantum computers to simulate both linear and nonlinear dynamics in greater detail. Because quantum computers can only efficiently perform linear operations on the quantum state, it is challenging to perform nonlinear operations that are generically required to describe the nonlinear differential equations of interest. In this work, we extend previous results on embedding nonlinear systems within linear systems by explicitly deriving the connection between the Koopman evolution operator, the Perron-Frobenius evolution operator, and the Koopman-von Neumann evolution (KvN) operator. We also explicitly derive the connection between the Koopman and Carleman approaches to embedding. Extension of the KvN framework to the complex-analytic setting relevant to Carleman embedding, and the proof that different choices of complex analytic reproducing kernel Hilbert spaces depend on the choice of Hilbert space metric are covered in the appendices. Finally, we conclude with a review of recent quantum hardware implementations of algorithms on present-day quantum hardware platforms that may one day be accelerated through Hamiltonian simulation. We discuss the simulation of toy models of wave-particle interactions through the simulation of quantum maps and of wave-wave interactions important in nonlinear plasma dynamics.Comment: 42 pages; 12 figures; invited paper at the 2021-2022 International Sherwood Fusion Theory Conferenc