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Ab-initio variational wave functions for the time-dependent many-electron Schrödinger equation (2403.07447v3)

Published 12 Mar 2024 in cond-mat.str-el, cs.LG, physics.chem-ph, physics.comp-ph, and quant-ph

Abstract: Understanding the real-time evolution of many-electron quantum systems is essential for studying dynamical properties in condensed matter, quantum chemistry, and complex materials, yet it poses a significant theoretical and computational challenge. Our work introduces a variational approach for fermionic time-dependent wave functions, surpassing mean-field approximations by accurately capturing many-body correlations. Therefore, we employ time-dependent Jastrow factors and backflow transformations, which are enhanced through neural networks parameterizations. To compute the optimal time-dependent parameters, we utilize the time-dependent variational Monte Carlo technique and a new method based on Taylor-root expansions of the propagator, enhancing the accuracy of our simulations. The approach is demonstrated in three distinct systems. In all cases, we show clear signatures of many-body correlations in the dynamics. The results showcase the ability of our variational approach to accurately capture the time evolution, providing insight into the quantum dynamics of interacting electronic systems, beyond the capabilities of mean-field.

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Citations (6)
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Summary

  • The paper introduces a variational approach that overcomes mean-field limitations by accurately capturing many-body electron correlations.
  • It employs time-dependent variational Monte Carlo with Jastrow factors, backflow transformations, and neural networks to solve the TDSE.
  • Results across harmonic models, molecular systems, and quantum dots demonstrate enhanced accuracy in simulating complex quantum dynamics.

A Novel Variational Approach for Simulating Time-dependent Many-electron Systems

Introduction

The paper of many-electron systems is pivotal for understanding a myriad of phenomena in quantum chemistry and condensed matter physics. Traditional methods, such as time-dependent Hartree-Fock (TDHF), though widely used, often fall short in accurately capturing the complexities of electron-electron interactions due to their mean-field nature. In this context, the paper by Jannes Nys, Gabriel Pescia, and Giuseppe Carleo presents a significant advancement by introducing a variational methodology to simulate the time evolution of many-electron systems, going beyond mean-field approximations. Their approach, which employs time-dependent variational Monte Carlo (tVMC) with a focus on incorporating many-body correlations using Jastrow factors and backflow transformations, opens new avenues for studying quantum dynamics in an array of systems.

Methodology

The authors detail a comprehensive methodological framework to approximate the time-evolving state of a quantum system governed by the time-dependent Schrödinger equation (TDSE). Their key innovation lies in parameterizing the wave function's evolution, facilitated by the implementation of time-dependent variational principles (TDVP), specifically MacLachlan's variational principle. Through tVMC, this approach enables efficient computation of optimal time-dependent parameters, overcoming the previous limitations encountered in describing real-time quantum dynamics.

Wave-function Models

The paper elaborates on the construction of variational wave-function models adapted for fermionic systems, featuring time-dependent Jastrow factors and backflow transformations to account for electron correlations. Furthermore, the integration of neural networks provides a novel avenue for parameterizing these functions, showcasing the fusion of traditional variational techniques with contemporary machine learning methodologies.

Results

The efficacy of the proposed method is demonstrated across three distinct systems, namely:

  1. The Harmonic Interaction Model: Showcasing clear signatures of many-body correlations in dynamics not captured by mean-field methods.
  2. Dynamics of a Diatomic Molecule in Intense Laser Fields: Illustrating the method's capability to accurately capture time-evolution in complex molecular systems.
  3. Quenched Quantum Dot: Highlighting the importance of including many-body correlations for understanding strongly interacting electronic systems.

The results underline the significant advantage of the variational approach in accurately capturing the quantum dynamics beyond the capabilities offered by mean-field approximations.

Conclusions and Future Work

This paper establishes a groundbreaking variational framework that effectively captures the time evolution of many-electron systems, marking a significant step forward in the simulation of quantum dynamics. The inclusion of many-body correlations opens up new possibilities for detailed investigations into the electronic structure of materials and molecules. Looking ahead, this method sets the stage for future explorations into larger systems and more complex scenarios, potentially revolutionizing our understanding of quantum materials and reactions.

The presented work emphasizes the ongoing evolution of computational methods in quantum physics, highlighting the convergence of traditional physics-based models and modern computational techniques. It paves the way for more sophisticated and accurate simulations, which are crucial for advancing our understanding of quantum systems.