Nonadiabatic molecular dynamics: Validation of the multiple spawning method for a multidimensional problem

1998/05/01 by M. Ben-Nun, Todd J. Martı́nez · 7 citations
Physics and Astronomy · #Advanced Chemical Physics Studies #Quantum, superfluid, helium dynamics #Spectroscopy and Quantum Chemical Studies

paper · doi:10.1063/1.476142

openalex publication_date 1998/05/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/26

Abstract

The recently introduced full multiple spawning (FMS) method for molecular dynamics beyond the Born–Oppenheimer approximation is tested against exact numerical solution of the coupled nuclear Schrödinger equation for a two-dimensional model problem with two electronic states. The method uses a multiconfigurational frozen Gaussian ansatz for the wave function and the key idea is to expand the size of the basis set only during nonadiabatic events, using available information to predict the regions of phase space where population will be created. This is accomplished via the spawning procedure which keeps the basis size manageable while ensuring that it provides a reasonable approximation to the exact wave function. The parameters that govern the numerical accuracy of the method are discussed in detail. Expectation values and branching ratios are predicted quantitatively over a broad range of energies.

Citations

• Distribution functions in physics: Fundamentals
• Quantal phase factors accompanying adiabatic changes
• Quantum mechanics as a statistical theory
• On the Quantum Correction For Thermodynamic Equilibrium

Cited by

• Ab Initio Multiple Spawning: Photochemistry from First Principles Quantum Molecular Dynamics
• Conical Intersections and Electronic Momentum As Viewed From Phase Space Electronic Structure Theory
• Conical intersection dynamics in solution: The chromophore of Green Fluorescent Protein
• The transfer of energy between electrons and ions in solids
• Quantum Dynamics from Classical Trajectories
• Variance of the energy of a quantum system in a time-dependent perturbation: Determination by nonadiabatic transition probabilities
• Ab initio multiple spawning [wikipedia]