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

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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

WavePacket flowchart
WavePacket flowchart
  • 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

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 , along with the energies , are obtained as solutions of the TISE

Their dynamics is obtained as solution of the TDSE (wikidata:Q165498)

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.

Variables

Using atomic units (wikidata:Q757568) throughout WavePacket software

Name Symbol Unit
number of bound states n.a.
initial time a. t. u.
final time a. t. u.
size of main time steps a. t. u.
number of sub steps n.a.
initial state n.a.

Parameters

Definition of WavePacket's standard Hamiltonian. If applicable, interaction with external electric fields through dipole moments and/or polarizabilities is treated within the semi-classical dipole approximation (TDSE only).

Name Symbol Unit
spatial discretization Bohr
kinetic energy Hartree
potential energy Hartree
absorbing potential Hartree
electric field a. u.
dipole moment a. u.
polarizability a. u.

Process Informationen

Process Steps

Essentially the same as above, thus doubling information given in section "Procedure" ?!?

Name Description Input Output Method Parameter Environment Mathematical Area
qm_setup Setup before simulations --- WavePacket object --- --- Matlab ---
qm_init Initialize specific simulation Set all input and parameters Initial state --- --- Matlab ---
qm_bound Stationary wave functions Choose number of bound states Bound states , energies Solving the TISE, see below All of the above parameters Matlab Numerical Mathematics
qm_propa Propagate wave functions Choose numerical propagator Intermediate and final states Solving the TDSE, see below All of the above parameters Matlab Numerical Mathematics
qm_cleanup Purge after simulations --- --- --- --- Matlab ---

Applied Methods

The WavePacket software packages encompasses several different methods for numerical propagation of quantum states in time. Due to the object-oriented concept and the open architecture, it is straightforward to add new classes for the implementation of further numerical schemes. The aim could/should be to evolve WavePacket into a "laboratory" for numerical quantum dynamics.

Solving the TISE

ID Name Process Step Parameter implemented by
wikidata:Q52069558 Fourier grid Hamiltonian qm_bound WavePacket Software

Solving the TDSE

ID Name Process Step Parameter implemented by
wikidata:Q2311789 Split-step method qm_propa Time step WavePacket Software
wikidata:Q115616698 Chebychev method qm_propa Time step WavePacket Software
wikidata:Q115616932 Second order differencing qm_propa Time step WavePacket Software

Note: WikiData entries for the latter two numerical methods were created by me (B. S.)

Software used

Software package: WavePacket project at SourceForge. This document is mainly on the mature and stable Matlab/Octave version of WavePacket. Note that there is also a C++/Python version which is still in an experimental phase (but making good progress recently). Both versions come with extended Wiki pages hosted along with the respective Sourceforge repositories.

ID Name Description Version Programming Language Dependencies versioned published documented
SF.net WavePacket Numerical quantum dynamics 7.0.0 Matlab/Octave n.a. git, svn see below Wiki
SF.net WavePacket Numerical quantum dynamics 0.3.4 C++/Python Tensor, Boost.Numeric.Odeint, pybind11, numpy, matplotlib git no Wiki

Extensive documentation is also available from this scientific article:

Hardware

WavePacket should run on any hardware for which Matlab (and a licence) is available

ID Name Processor Compiler #Nodes #Cores

Input Data

All the input needed for a WavePacket simulation is encoded in a Matlab script called qm_init.m which has to be provided by the user. A large number of existing demo examples are expected to be very helpful for unexperienced users. Essentially, the input data therein match everything given above, see sections on "Variables" and "Parameters".

ID Name Size Data Structure Format Representation Format Exchange binary/text proprietary to publish to archive
- qm_init.m tiny [kB] Matlab script - m-file text yes yes yes

Output Data

ID Name Size Data Structure Format Representation Format Exchange binary/text proprietary to publish to archive
- Log output, e.g. qm_propa.out tiny [kB] - - txt-file text no no yes
- Wave functions: large [GB] - - mat-file binary yes no perhaps
- Snapshots small [MB] - - fig binary yes yes yes
- Snapshots small [MB] - - jpg binary no yes yes
- Animation small [MB] - - mp4 binary no perhaps yes

Reproducibility

Mathematical Reproducibility

WavePacket reproduces several known analytic solutions of Schrödinger equations, see the demo examples on our Wiki pages. Among them well-known cases such as the quantum harmonic oscillator and the Morse oscillator, but also less widespread ones such as the generalized pendulum which is an intriguing example for conditionally quasi-exactly solvability (CQES), see wikidata:Q25111852 and our 2017 work, wikidata:Q59528631.

Runtime Reproducibility

Not sure what to write here

Reproducibility of Results

Not sure what to write here

Reproducibility on original Hardware

Originally developed on Windows-PCs. No changes of the results upon migrating from Win7 to Win10 and Win11. (No surprise because it is Matlab!)

Reproducibility on other Hardware

Reproducibility is ensured for Linux and iOS. (No surprise because it is Matlab!)

a) Serial Computation

b) Parallel Computation

So far, no specific efforts were taken to make WavePacket suitable for parallel computation. However, at least on multi-core-CPUs Matlab automatically uses several cores, e.g., when doing Fourier transforms or standard Linear Algebra tasks.

Transferability to

a) similar model parameters (other initial and boundary values):

The WavePacket program package comes with a choice of different model functions for

If none of the provided model functions fits, the user has the choice either to write new ones or to provide tabulated data (→interpolation)

b) other models: Simulations of classical and quantum-classical dynamics also available within WavePacket using the same input, thus simulating exactly the same physical system. (This is a unique selling point)

Legend

The following abbreviations are used in the document to indicate/resolve IDs:

doi: DOI / https://doi.org/

sw: swMATH / https://swmath.org/software/

zb: zbMATH / https://zbmath.org/

wikidata: https://www.wikidata.org/wiki/