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Quantum time-dependent statistical mechanics

Mark E. Tuckerman

Published Aug 1, 2023• 1 citation
Publisher

Abstract

Abstract Chapter 14 covers the statistical mechanics of driven quantum systems and the non-equilibrium ensembles associated with them. The topic is presented both from the state-vector and density matrix perspectives. The chapter begins with a discussion of driving forces resulting from light-matter interactions and their treatment via time-dependent perturbation theory. The Fermi Golden Rule is derived, and it is shown how to incorporate the Golden Rule into the calculation of frequency spectra within the canonical ensemble, which then connects to canonical quantum time correlation functions. The formalism is derived again from the quantum Liouville equation. The discussion then turns to the challenge of computing quantum time correlation functions and approximate techniques based on the Feynman path integral of Chapter 12. These schemes include centroid and ring-polymer molecular dynamics as well as open-path integral methods

DOI
10.1093/oso/9780198825562.003.0014

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Abstract Chapter 14 covers the statistical mechanics of driven quantum systems and the non-equilibrium ensembles associated with them. The topic is presented both from the state-vector and density matrix perspectives. The chapter begins with a discussion of driving forces resulting from light-matter interactions and their treatment via time-dependent perturbation theory. The Fermi Golden Rule is derived, and it is shown how to incorporate the Golden Rule into the calculation of frequency spectra within the canonical ensemble, which then connects to canonical quantum time correlation functions. The formalism is derived again from the quantum Liouville equation. The discussion then turns to the challenge of computing quantum time correlation functions and approximate techniques based on the Feynman path integral of Chapter 12. These schemes include centroid and ring-polymer molecular dynamics as well as open-path integral methods
Abstract The focus of Chapter 12 is the Feynman path integral formulations of quantum mechanics and quantum statistical mechanics. The connection between real-time quantum propagator and the density matrix is established via the Wick rotation, and a Trotter expansion is used to derive discrete path integral expressions for both. The continuous limit of the discrete path integral is derived to yield the functional integral formulation of the path integral. The construction of estimators and their averages for computing quantum observables is discussed. Next, the path integral is extended to incorporate Boltzmann, Fermi-Dirac, and Bose-Einstein statistics, and a useful recursive formula for the partition function is derived that accelerates convergence by building up N-body partition functions from those of smaller systems. Quantum free energies are discussed, and algorithms for the evaluation of path integrals using molecular dynamics or Monte Carlo are presented. The chapter concludes with a discussion of higher-order factorizations and ring-polymer contraction methods to reduce the computational overhead of path-integral calculations
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Abstract In this chapter we review time-independent and time-dependent perturbation theory in quantum mechanics. We begin with Rayleigh-Schrödinger perturbation theory for small corrections to the Hamiltonian for non-degenerate and degenerate spectra, which leads us to a discussion of avoided crossings. We then apply these methods to calculate the fine-structure corrections for the energy levels of the hydrogen atom, including the relativistic correction to the kinetic energy, the spin-orbit correction, and the Darwin term. We then turn to the effect of weak constant magnetic fields: for the resulting Zeeman effect we distinguish between the anomalous Zeeman effect and the Paschen-Back effect. In the context of the corresponding Stark effect for electric fields we introduce the Wigner-Eckart theorem and calculate perturbations to first and second order. We then turn to time-independent problems and discuss the Born-von Neumann series for the propagator, time-ordered integrals, the interaction picture, before explaining Fermi’s golden rule.
Quantum time correlation functions are often the principal objects of interest in experimental investigations of the dynamics of quantum systems. For instance, transport properties, such as diffusion and reaction rate coefficients, can be obtained by integrating these functions. The evaluation of such correlation functions entails sampling from quantum equilibrium density operators and quantum time evolution of operators. For condensed phase and complex systems, where quantum dynamics is difficult to carry out, approximations must often be made to compute these functions. We present a general scheme for the computation of correlation functions, which preserves the full quantum equilibrium structure of the system and approximates the time evolution with quantum-classical Liouville dynamics. Several aspects of the scheme are discussed, including a practical and general approach to sample the quantum equilibrium density, the properties of the quantum-classical Liouville equation in the context of correlation function computations, simulation schemes for the approximate dynamics and their interpretation and connections to other approximate quantum dynamical methods.
How to deal with time-dependent potentials, what kinds of physical problems having time-dependent potentials can be solved exactly and which are to be solved with the use of perturbation theory, what are different possible forms of time-dependent perturbating fields, and semi-classical treatment of the interaction of fields with matter are the subject matters of this chapter. First order perturbation theory, computation of transition probability, transition rates and Fermi's Golden Rule for harmonic and constant perturbations, absorption, stimulated emission and dipole approximation when electromagnetic fields interact with matter, spontaneous emission and Einstein coefficients, and dipole selection rules are other topics which are dealt with in detail in the chapter. Discussions with properly justified mathematical treatment on time-dependent potentials and on the exactly solvable time-dependent two-state systems are the special foci of this chapter.
We introduce a new approach for calculating quantum time-correlation functions and time-dependent expectation values in many-body thermal systems; both electronically adiabatic and non-adiabatic cases can be treated. Our approach uses a path integral simulation to sample an initial thermal density matrix; subsequent evolution of this density matrix is equivalent to solution of the time-dependent Schrödinger equation, which we perform using a linear expansion of Gaussian wavepacket basis functions which evolve according to simple classical-like trajectories. Overall, this methodology represents a formally exact approach for calculating time-dependent quantum properties; by introducing approximations into both the imaginary-time and real-time propagations, this approach can be adapted for complex many-particle systems interacting through arbitrary potentials. We demonstrate this method for the spin Boson model, where we find good agreement with numerically exact calculations. We also discuss future directions of improvement for our approach with a view to improving accuracy and efficiency.