Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. Journal articles
  4. Family of Gaussian wavepacket dynamics methods from the perspective of a nonlinear Schrodinger equation
 
research article

Family of Gaussian wavepacket dynamics methods from the perspective of a nonlinear Schrodinger equation

Vanicek, Jiri J. L.  
July 7, 2023
Journal Of Chemical Physics

Many approximate solutions of the time-dependent Schrodinger equation can be formulated as exact solutions of a nonlinear Schrodinger equation with an effective Hamiltonian operator depending on the state of the system. We show that Heller's thawed Gaussian approximation, Coalson and Karplus's variational Gaussian approximation, and other Gaussian wavepacket dynamics methods fit into this framework if the effective potential is a quadratic polynomial with state-dependent coefficients. We study such a nonlinear Schrodinger equation in full generality: we derive general equations of motion for the Gaussian's parameters, demonstrate time reversibility and norm conservation, and analyze conservation of energy, effective energy, and symplectic structure. We also describe efficient, high-order geometric integrators for the numerical solution of this nonlinear Schrodinger equation. The general theory is illustrated by examples of this family of Gaussian wavepacket dynamics, including the variational and nonvariational thawed and frozen Gaussian approximations and their special limits based on the global harmonic, local harmonic, single-Hessian, local cubic, and local quartic approximations for the potential energy. We also propose a new method by augmenting the local cubic approximation with a single fourth derivative. Without substantially increasing the cost, the proposed "single-quartic" variational Gaussian approximation improves the accuracy over the local cubic approximation and, at the same time, conserves both the effective energy and symplectic structure, unlike the much more expensive local quartic approximation. Most results are presented in both Heller's and Hagedorn's parametrizations of the Gaussian wavepacket.

  • Details
  • Metrics
Type
research article
DOI
10.1063/5.0146680
Web of Science ID

WOS:001025227400015

Author(s)
Vanicek, Jiri J. L.  
Date Issued

2023-07-07

Published in
Journal Of Chemical Physics
Volume

159

Issue

1

Article Number

014114

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

wave-packet dynamics

•

nonadiabatic molecular-dynamics

•

initio semiclassical evaluation

•

quantum dynamics

•

composition constants

•

value representation

•

vibronic spectra

•

energy

•

operators

•

systems

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

Available on Infoscience
August 28, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/200084
Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés