Numerical quantum dynamics using WavePacket: II. Open quantum systems, optimal control, and model reduction

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

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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.

Procedure

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• 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 $\rho (t)$

$i\frac{\partial }{\partial t}\rho (t)=[H(R,-i{\mathrm{\nabla }}_R,t),\rho (t)]$

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	$n_{\mathrm{m}\mathrm{a}\mathrm{x}}$	n.a.
initial time	$t_0$	a. t. u.
final time	$t_f$	a. t. u.
size of main time steps	$\mathrm{\Delta }t$	a. t. u.
number of sub steps	$n$	n.a.
initial state	${\mathrm{\Psi }}_0$	n.a.
decay rates	$\mathrm{\Gamma }$	1 / a.t.u.
dimension of truncated model	$$ through dipole moments $\mu (R)$ and/or polarizabilities $\alpha (R)$ is treated within the semi-classical dipole approximation. $H=T(R,-i{\mathrm{\nabla }}_R)1+V(R)-iW(R)1-F(t)\cdot \mu (R)-\frac{1}{2}{F}^2(t)\cdot \alpha (R)$ Name Symbol Unit spatial discretization $R$ Bohr kinetic energy $T(-i{\mathrm{\nabla }}_R,R)$ 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. system-bath-coupling $C_{ij}$ 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 $\mathrm{\Psi }(t_i)$ or $\rho (t_i)$ 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 $\mathrm{\Psi }(t_i)$ or $\rho (t_i)$ 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: $\mathrm{\Psi }(t),\rho (t)$ 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 $T(-i{\mathrm{\nabla }}_R,R)$ 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 $\mathrm{\Psi }(t=0)$ System-bath-coupling $C_{ij}$ 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/