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arXiv:2205.02358 · Journal of Chemical Theory and Computation

Variational Approach for Linearly Dependent Moving Bases in Quantum Dynamics: Application to Gaussian Functions

Loïc Joubert-Doriol

Published Sep 27, 2022• 6 citations
arXivHTMLPDF

Abstract

In this paper, we present a variational treatment of the linear dependence for a non-orthogonal time-dependent basis set in solving the Schrödinger equation. The method is based on (i) the definition of a linearly independent working space and (ii) a variational construction of the propagator over finite time steps. The second point allows the method to properly account for changes in the dimensionality of the working space along the time evolution. In particular, the time evolution is represented by a semi-unitary transformation. Tests are carried out on a quartic double-well potential with Gaussian basis functions whose centers evolve according to classical equations of motion. We show that the resulting dynamics converges to the exact one and is unitary by construction.

DOI
10.1021/acs.jctc.2c00461

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Development of a general approach to construction of efficient high-dimensional bases is an outstanding challenge in quantum dynamics describing large amplitude motion of molecules and fragments. A number of approaches, proposed over the years, utilize Gaussian bases whose parameters are somehow-usually by propagating classical trajectories or by solving coupled variational equations-tailored to the shape of a wave function evolving in time. In this paper we define the time-dependent Gaussian bases through an ensemble of quantum or Bohmian trajectories, known to provide a very compact representation of a wave function due to conservation of the probability density associated with each trajectory. Though the exact numerical implementation of the quantum trajectory dynamics itself is, generally, impractical, the quantum trajectories can be obtained from the wave function expanded in a basis. The resulting trajectories are used to guide compact Gaussian bases, as illustrated on several model problems.
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Abstract An effective operational approach to quantum mechanics is to focus on the evolution of wave packets, for which the wave function can be seen in the semi-classical regime as representing a classical motion dressed with extra degrees of freedom describing the shape of the wave packet and its fluctuations. These quantum dressing are independent degrees of freedom, mathematically encoded in the higher moments of the wave function. We review how to extract the effective dynamics for Gaussian wave packets evolving according to the Schrödinger equation with time-dependent potential in a 1 + 1-dimensional spacetime, and derive the equations of motion for the quadratic uncertainty. We then show how to integrate the evolution of all the higher moments for a general wave function in a time-dependent harmonic potential.
The behavior of a particle moving according to the laws of quantum mechanics in a field, which potential changes over time, is studied. The method of unitary transformations for solving the temporal Schrödinger equation is considered. The reduced Hamiltonian of the system of a quantum­-mechanical particle in time­-dependent potential is obtained, as well as the total operator of the evolution of such a system. We find a new version of the unitary transformation, which, compared to the known ones, simplifies solving the problem in analytical form. This transformation associates the linear potential quantum model with time-­dependent parameters and free­particle system. Based on the constructed evolution operator, we consider the wave packet dispersion. It is shown that the wave packet dispersion for this model is the same as that for a free particle. This conclusion is the general result of the behavior of a quantum­mechanical particle moving in the field of a time­dependent linear potential.
This project looks into the time evolution of a wave function within a two-dimensional quantum well. We start by solving the time-dependent Schrödinger equation for stationary states in a quantum well. Next, we express any wave function as a linear combination of stationary states, allowing us to understand their time evolution. Two methods are presented: one relies on decomposing the wave function into a basis of stationary states and the other on discretisation of the time-dependent Schrödinger equation, incorporating three-point formulas for derivatives. These approaches necessitate confronting intricate boundary conditions and require maintaining energy conservation for numerical accuracy. We further demonstrate the methods using a wave packet, revealing fundamental phenomena in quantum physics. Our results demonstrate the utility of these methods in understanding quantum systems, despite the challenges in determining stationary states for a given potential. This study enhances our comprehension of the dynamics of quantum states in constrained systems, essential for fields like quantum computing and nanotechnology.