Author: Burkhard Schmidt, ORCID:0000-0002-9658-499X, personal web page: www.qcmd.info
Publication listed at zbMATH
Software not yet listed at swMATH

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.

Procedure

qm_matrix: Generate matrix (state space) representations of relevant operators
qm_abncd: Setup bilinear control problem, either for TDSE or for LvNE
qm_balance: Perform balancing transformation of controllability and observability
qm_truncate: Perform simple truncation of balanced representation or singular perturbation approximation
qm_H2model: Perform H2 optimal model reduction
qm_propa: Propagation of full or reduced system without given temporal profile of control fields
qm_optimal: Propagation of full or reduced system with optimization of temporal profile of control fields

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. Perhaps a cooperation with Benner/Saak at MPI-DCTS?

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

For the case of molecules in thermal contact with their environment (e.g. molecules in solution phase or impurities in a solid), the Liouville-von Neumann equation (LvNE, wikidata:Q2533076) with Lindblad operators describing dephasing and|or dissipation has to be solved for the density operator|matrix $ρ (t)$

$i \frac{\partial}{\partial t} ρ (t) = [H (R, - i \nabla_{R}, t), ρ (t)]$

Discretization

Time: Equally spaced time steps; typically to be chosen inversely proportional to the spectrum of the Hamiltonian.
Space: A state space (aka energy space) representation is used here, based on bound states calculated with qm_bound, see quantum dynamics workflow I.

Variables

Using atomic units (wikidata:Q757568) throughout WavePacket software

Name

Symbol

Unit

number of bound states

n_{m a x}

n.a.

initial time

t_{0}

a. t. u.

final time

t_{f}

a. t. u.

size of main time steps

Δ t

a. t. u.

number of sub steps

n

n.a.

initial state

Ψ_{0}

n.a.

decay rates

Γ

1 / a.t.u.

dimension of truncated model

through dipole moments

μ (R)

and/or polarizabilities

α (R)

is treated within the semi-classical dipole approximation.

$H = T (R, - i \nabla_{R}) 1 + V (R) - i W (R) 1 - F (t) \cdot μ (R) - \frac{1}{2} F^{2} (t) \cdot α (R)$

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	$μ (R)$	a. u.
polarizability	$α (R)$	a. u.
system-bath-coupling	$C_{i j}$	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_matrix	Generate matrix representations	Cutoff for setting matrix elements to zero	Matrix elements of quantum operators	Numerical quadratures	Most of the above parameters	Matlab	Numerical Mathematics
qm_abncd	Setup bilinear control problem	Matrix elements of quantum operators	Matrices A,B,N,C,D used in bilinear control	TDSE or LvNE with dephasing, dissipation	Decay rates	Matlab	Quantum mechanics
qm_balance	Perform balancing transformation	Unbalanced matrices A,B,N,C,D	Balanced matrices A',B',N',C',D'	Balancing controllability vs. observability	n. a.	Matlab	Model order reduction
qm_truncate	Truncate balanced representation	Balanced matrices A',B',N',C',D'	Truncated matrices A,B,N,C,D	Truncation or singular perturbation theory	dimension of truncated model	Matlab	Model order reduction
qm_H2model	Perform H2 optimal model reduction	Full matrices A,B,N,C,D	Reduced matrices A',B',N',C',D'	ℋ2-Optimal Model Reduction	dimension of reduced model	Matlab	Model order reduction
qm_propa	Propagation with given control fields	Choose ODE solver	Intermediate and final states $Ψ (t_{i})$ or $ρ (t_{i})$	Solving sets of coupled ODEs	Matrices A,B,N,C,D	Matlab	Numerical Mathematics
qm_optimal	Optimization of control fields	Choose ODE solver	Intermediate and final states $Ψ (t_{i})$ or $ρ (t_{i})$	Optimal control of quantum system	Matrices A,B,N,C,D	Matlab	Optimal control theory

Applied Methods

The WavePacket software packages encompasses several different methods for solving sets of coupled ordinary differential equations (ODEs) 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.

ID	Name	Process Step	Parameter	implemented by
wikidata:Q1028945	Generalized Lyapunov equation	qm_balance	convergence of iteration	WavePacket Software
wikidata:Q3730848	Generalized Sylvester equation	qm_H2model	convergence of iteration	WavePacket Software
wikidata:Q725944	Runge-Kutta ODE solvers	qm_propa	time steps	WavePacket Software
wikidata:Q57604851	Quantum Optimal Control Theory	qm_optimal	time steps, initial guess of control fields	WavePacket Software

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	n.a.	git	no	Wiki

Extensive documentation is also available from this scientific article:

Comp. Phys. Comm. (2018), doi:10.1016/j.cpc.2018.02.022

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	tiny [kB]	Matlab script	m-file	wiki	text	yes	yes	yes

Output Data

ID	Name	Size	Data Structure	Format Representation	Format Exchange	binary/text	proprietary	to publish	to archive
-	Log output: qm_xyz.out	tiny [kB]	-	txt	-	text	no	no	yes
-	Optimal control field: $F (t)$	medium [MB]	-	mat	-	binary	yes	no	yes
-	Wave functions/densities: $Ψ (t), ρ (t)$	large [GB]	-	mat	-	binary	yes	no	perhaps
-	Figures	small [MB]	-	jpg, fig	-	binary	no	yes	yes
-	Animation	small [MB]	-	mp4	-	binary	no	perhaps	yes

Reproducibility

Mathematical Reproducibility

Not sure what to write here

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 $μ (R)$
Polarizability tensor $α (R)$
Initial quantum states $Ψ (t = 0)$
System-bath-coupling $C_{i j}$

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: II. Open quantum systems, optimal control, and model reduction

Contents

Problem Statement

Object of Research and Objective

Procedure

Involved Disciplines

Data Streams

Model

Discretization

Variables

Process Informationen

Process Steps

Applied Methods

Software used

Hardware

Input Data

Output Data

Reproducibility

Mathematical Reproducibility

Runtime Reproducibility

Reproducibility of Results

Reproducibility on original Hardware

Reproducibility on other Hardware

Transferability to

Legend