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

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

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 $\Psi _{n}(R)$ , along with the energies $E_{n}$ , are obtained as solutions of the TISE

${\hat {H}}(R,-i\nabla _{R},t)\Psi _{n}(R)=E_{n}\Psi _{n}(R)$

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

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

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.

Variables

Using atomic units (wikidata:Q757568) throughout WavePacket software

Name	Symbol	Unit
number of bound states	$n_{\mathrm {max} }$	n.a.
initial time	$t_{0}$	a. t. u.
final time	$t_{f}$	a. t. u.
size of main time steps	$\Delta t$	a. t. u.
number of sub steps	$n$	n.a.
initial state	$\Psi _{0}$	n.a.

Parameters

Definition of WavePacket's standard Hamiltonian. If applicable, interaction with external electric fields $F(t)$ through dipole moments $\mu (R)$ and/or polarizabilities $\alpha (R)$ is treated within the semi-classical dipole approximation (TDSE only).

$H=T(R,-i\nabla _{R})1+V(R)-iW(R)1-F(t)\cdot \mu (R)-{\frac {1}{2}}F^{2}(t)\cdot \alpha (R)$

Name	Symbol	Unit
spatial discretization	$R$	Bohr
kinetic energy	$T(-i\nabla _{R},R)$	Hartree
potential energy	$V(R,t)$	Hartree
absorbing potential	$W(R)$	Hartree
electric field	$F(t)$	a. u.
dipole moment	$\mu (R)$	a. u.
polarizability	$\alpha (R)$	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 $\Psi (t_{0})$	---	---	Matlab	---
qm_bound	Stationary wave functions	Choose number of bound states	Bound states $\Psi _{n}$ , energies $E_{n}$	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 $\Psi (t_{i})$	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	$n_{\mathrm {max} }$	WavePacket Software

Solving the TDSE

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

Comp. Phys. Comm. (2017), doi:10.1016/j.cpc.2016.12.007

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: $\Psi _{n},\Psi (t)$	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

Kinetic energy operators $T(-i\nabla _{R},R)$
Potential energy functions $V(R)$
Negative imaginary potentials $W(R)$
Pulse shapes for electric fields $F(t)$
(Permanent or transition) dipole moments $\mu (R)$
Polarizability tensor $\alpha (R)$
Initial quantum states $\Psi (t=0)$

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/

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

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