Numerical quantum dynamics using WavePacket: I. Closed quantum systems and discrete variable representations

• Author: Burkhard Schmidt, ORCID:0000-0002-9658-499X, personal web page: www.qcmd.info
• Publication also listed at zbMATH:1376.81005
• Software also listed at swMATH:19829

Problem Statement

Numerical quantum dynamics, wikidata:Q7269042

For atoms, molecules and possible also other fields, including interaction of quantum systems with external fields within the semi-classical dipole approximation

Object of Research and Objective

Although WavePacket is made for general quantum systems, so far it has been developed/used mainly for describing the dynamics of molecules, i.e., typically the motion of the comprising nuclei. Especially when low masses (e.g. hydrogen atoms), low energies, and/or low temperatures are involved, the dynamics of the nuclei may be subject to quantum effects. Hence, the modeling of small molecules should be based on quantum mechanical modeling. Because of the computational effort increasing steeply (exponentially?) with the number of atoms, this can not be done for large molecules. However, due to recent advances both in computer hardware and in modeling/algorithms, the border between small and large is constantly shifting toward the latter ...

Procedure

<img src="flowchart.jpg" width="500" height="100">

• qm_setup: Before WavePacket simulations, initialize a wave function object.
• qm_init: Initialize your simulation scenario, i.e. potential and kinetic energy operators, spatial and temporal discretization, coupling to external fields, set initial state.
• qm_bound: Solving the time-independent Schrödinger equation (TISE), i.e., calculate stationary bound states of a quantum system. Note that there is a substantial choice of spatial discretizations built-in for numerical solution of the TISE.
• qm_propa: Solving the time-dependent Schrödinger equation (TDSE), i.e., propagate the state of a quantum state in time. Note that there is a substantial choice of different integration methods built-in for numerical solution of the TDSE.
• qm_cleanup: After WavePacket simulations, clean up everything ...

Involved Disciplines

• Theoretical Chemistry, wikidata:Q321150
• Femto-chemistry, see, e.g., 1996 nobel prize in chemistry for A.H.Zewail, wikidata:Q106624
• Molecular physics, wikipedia:Q489328

Connection to other MaRDI projects and to other NFDI consortia yet to be established

Data Streams

Not sure what to write here. In some of the other workflows, data streams from and to projects in other consortia are mentioned here

Model

Isolated molecules (e.g. single molecules in electric, magnetic, optical traps, or in dilute gases), can be modeled as closed quantum systems. Their bound states $\Psi_n$, along with the energies $E_n$, are obtained as solutions of the TISE

$\hat{H}(R,-i{\mathrm{\nabla }}_R,t){\mathrm{\Psi }}_n=E_n{\mathrm{\Psi }}_n$

Their dynamics is obtained as solution $\Psi(t)$ of the TDSE (wikidata:Q165498)

$i\frac{\partial }{\partial t}\mathrm{\Psi }(t)=\hat{H}(R,-i{\mathrm{\nabla }}_R,t)\mathrm{\Psi }(t)$

Discretization

• Time (TDSE only): Equally spaced time steps; typically to be chosen inversely proportional to the spectrum of the spatially discretized Hamiltonian.
• Space: For each degree of freedom there is a choice of the following pseudo-spectral discretizations
  • FFT methods, with equally spaced grid points: Mainly for molecular scattering, dissociation, association
  • Gauss-Hermite: Mainly for molecular vibrations
  • Gauss-Legendre: Mainly for molecular rotations

Due to the object-oriented concept and the open architecture, it is straightforward to add new classes for spatial discretizations.