Non-normal Lanczos methods for quantum scattering

This article presents a new complex absorbing potential (CAP) block Lanczos method for computing scattering eigenfunctions and reaction probabilities. The method reduces the problem of computing energy eigenfunctions to solving two energy dependent systems of equations. An energy independent block Lanczos factorization casts the system into a block tridiagonal form, which can be solved very efficiently for all energies. We show that CAP-Lanczos methods exhibit instability due to the non-normality of CAP Hamiltonians and may break down for some systems. The instability is not due to loss of orthogonality but to non-normality of the Hamiltonian matrix. While use of a Woods-Saxon exponential CAP-as opposed to a polynomial CAP-reduced non-normality, it did not always ensure convergence. Our results indicate that the Arnoldi algorithm is more robust for non-normal systems and less prone to break down. An Arnoldi version of our method is applied to a nonadiabatic tunneling Hamiltonian with excellent results, while the Lanczos algorithm breaks down for this system.     

Quantum and electromagnetic propagation with the conjugate symmetric Lanczos method

The conjugate symmetric Lanczos (CSL) method is introduced for the solution of the time-dependent Schrodinger equation. This remarkably simple and efficient time-domain algorithm is a low-order polynomial expansion of the quantum propagator for time-independent Hamiltonians and derives from the time-reversal symmetry of the Schrodinger equation. The CSL algorithm gives forward solutions by simply complex conjugating backward polynomial expansion coefficients. Interestingly, the expansion coefficients are the same for each uniform time step, a fact that is only spoiled by basis incompleteness and finite precision. This is true for the Krylov basis and, with further investigation, is also found to be true for the Lanczos basis, important for efficient orthogonal projection-based algorithms. The CSL method errors roughly track those of the short iterative Lanczos method while requiring fewer matrix-vector products than the Chebyshev method. With the CSL method, only a few vectors need to be stored at a time, there is no need to estimate the Hamiltonian spectral range, and only matrix-vector and vector-vector products are required. Applications using localized wavelet bases are made to harmonic oscillator and anharmonic Morse oscillator systems as well as electrodynamic pulse propagation using the Hamiltonian form of Maxwell's equations. For gold with a Drude dielectric function, the latter is non-Hermitian, requiring consideration of corrections to the CSL algorithm.     

Two-dimensional quantum propagation using wavelets in space and time

A recent method for solving the time-dependent Schrodinger equation has been developed using expansions in compact-support wavelet bases in both space and time [H. Wang et al., J. Chem. Phys. 121, 7647 (2004)]. This method represents an exact quantum mixed time-frequency approach, with special initial temporal wavelets used to solve the initial value problem. The present work is a first extension of the method to multiple spatial dimensions applied to a simple two-dimensional (2D) coupled anharmonic oscillator problem. A wavelet-discretized version of norm preservation for time-independent Hamiltonians discovered in the earlier one-dimensional investigation is verified to hold as well in 2D and, by implication, in higher numbers of spatial dimensions. The wavelet bases are not restricted to rectangular domains, a fact which is exploited here in a 2D adaptive version of the algorithm.     

Multiscale quantum propagation using compact-support wavelets in space and time

Orthogonal compact-support Daubechies wavelets are employed as bases for both space and time variables in the solution of the time-dependent Schrodinger equation. Initial value conditions are enforced using special early-time wavelets analogous to edge wavelets used in boundary-value problems. It is shown that the quantum equations may be solved directly and accurately in the discrete wavelet representation, an important finding for the eventual goal of highly adaptive multiresolution Schrodinger equation solvers. While the temporal part of the basis is not sharp in either time or frequency, the Chebyshev method used for pure time-domain propagations is adapted to use in the mixed domain and is able to take advantage of Hamiltonian matrix sparseness. The orthogonal separation into different time scales is determined theoretically to persist throughout the evolution and is demonstrated numerically in a partially adaptive treatment of scattering from an asymmetric Eckart barrier.     

Multidimensional quantum trajectories: applications of the derivative propagation method

In a previous publication [J. Chem. Phys. 118, 9911 (2003)], the derivative propagation method (DPM) was introduced as a novel numerical scheme for solving the quantum hydrodynamic equations of motion (QHEM) and computing the time evolution of quantum mechanical wave packets. These equations are a set of coupled, nonlinear partial differential equations governing the time evolution of the real-valued functions C and S in the complex action, S=C(r,t) + iS(r,t)/Planck's over 2pi, where Psi(r,t)=exp(S). Past numerical solutions to the QHEM were obtained via ensemble trajectory propagation, where the required first- and second-order spatial derivatives were evaluated using fitting techniques such as moving least squares. In the DPM, however, equations of motion are developed for the derivatives themselves, and a truncated set of these are integrated along quantum trajectories concurrently with the original QHEM equations for C and S. Using the DPM quantum effects can be included at various orders of approximation; no spatial fitting is involved; there is no basis set expansion; and single, uncoupled quantum trajectories can be propagated (in parallel) rather than in correlated ensembles. In this study, the DPM is extended from previous one-dimensional (1D) results to calculate transmission probabilities for 2D and 3D wave packet evolution on coupled Eckart barrier/harmonic oscillator surfaces. In the 2D problem, the DPM results are compared to standard numerical integration of the time-dependent Schrodinger equation. Also in this study, the practicality of implementing the DPM for systems with many more degrees of freedom is discussed.     

Minimum-error method for scattering problems in quantum mechanics: Two stable and efficient implementations

We examine here, by using a simple example, two implementations of the minimum error method (MEM), a least-squares minimization for scattering problems in quantum mechanics, and show that they provide an efficient, numerically stable alternative to Kohn variational principle. MEM defines an error-functional consisting of the sum of the values of (HPsi - EPsi)2 at a set of grid points. The wave function Psi, is forced to satisfy the scattering boundary conditions and is determined by minimizing the least-squares error. We study two implementations of this idea. In one, we represent the wave function as a linear combination of Chebyshev polynomials and minimize the error by varying the coefficients of the expansion and the R-matrix (present in the asymptotic form of Psi). This leads to a linear equation for the coefficients and the R-matrix, which we solve by matrix inversion. In the other implementation, we use a conjugate-gradient procedure to minimize the error with respect to the values of Psi at the grid points and the R-matrix. The use of the Chebyshev polynomials allows an efficient and accurate calculation of the derivative of the wave function, by using Fast Chebyshev Transforms. We find that, unlike KVP, MEM is numerically stable when we use the R-matrix asymptotic condition and gives accurate wave functions in the interaction region.     

A multidimensional pseudospectral method for optimal control of quantum ensembles

In our previous work, we have shown that the pseudospectral method is an effective and flexible computation scheme for deriving pulses for optimal control of quantum systems. In practice, however, quantum systems often exhibit variation in the parameters that characterize the system dynamics. This leads us to consider the control of an ensemble (or continuum) of quantum systems indexed by the system parameters that show variation. We cast the design of pulses as an optimal ensemble control problem and demonstrate a multidimensional pseudospectral method with several challenging examples of both closed and open quantum systems from nuclear magnetic resonance spectroscopy in liquid. We give particular attention to the ability to derive experimentally viable pulses of minimum energy or duration.     

Monotonically convergent optimization in quantum control using Krotov's method

The non-linear optimization method developed by A. Konnov and V. Krotov [Autom. Remote Cont. (Engl. Transl.) 60, 1427 (1999)] has been used previously to extend the capabilities of optimal control theory from the linear to the non-linear Schr?dinger equation [S. E. Sklarz and D. J. Tannor, Phys. Rev. A 66, 053619 (2002)]. Here we show that based on the Konnov-Krotov method, monotonically convergent algorithms are obtained for a large class of quantum control problems. It includes, in addition to nonlinear equations of motion, control problems that are characterized by non-unitary time evolution, nonlinear dependencies of the Hamiltonian on the control, time-dependent targets, and optimization functionals that depend to higher than second order on the time-evolving states. We furthermore show that the nonlinear (second order) contribution can be estimated either analytically or numerically, yielding readily applicable optimization algorithms. We demonstrate monotonic convergence for an optimization functional that is an eighth-degree polynomial in the states. For the "standard" quantum control problem of a convex final-time functional, linear equations of motion and linear dependency of the Hamiltonian on the field, the second-order contribution is not required for monotonic convergence but can be used to speed up convergence. We demonstrate this by comparing the performance of first- and second-order algorithms for two examples.     

An efficient method for the calculation of quantum mechanics/molecular mechanics free energies

The combination of quantum mechanics (QM) with molecular mechanics (MM) offers a route to improved accuracy in the study of biological systems, and there is now significant research effort being spent to develop QM/MM methods that can be applied to the calculation of relative free energies. Currently, the computational expense of the QM part of the calculation means that there is no single method that achieves both efficiency and rigor; either the QM/MM free energy method is rigorous and computationally expensive, or the method introduces efficiency-led assumptions that can lead to errors in the result, or a lack of generality of application. In this paper we demonstrate a combined approach to form a single, efficient, and, in principle, exact QM/MM free energy method. We demonstrate the application of this method by using it to explore the difference in hydration of water and methane. We demonstrate that it is possible to calculate highly converged QM/MM relative free energies at the MP2/aug-cc-pVDZ/OPLS level within just two days of computation, using commodity processors, and show how the method allows consistent, high-quality sampling of complex solvent configurational change, both when perturbing hydrophilic water into hydrophobic methane, and also when moving from a MM Hamiltonian to a QM/MM Hamiltonian. The results demonstrate the validity and power of this methodology, and raise important questions regarding the compatibility of MM and QM/MM forcefields, and offer a potential route to improved compatibility.     

Optimal control of quantum non-Markovian dissipation: reduced Liouville-space theory

An optimal control theory for open quantum systems is constructed containing non-Markovian dissipation manipulated by an external control field. The control theory is developed based on a novel quantum dissipation formulation that treats both the initial canonical ensemble and the subsequent reduced control dynamics. An associated scheme of backward propagation is presented, allowing the efficient evaluation of general optimal control problems. As an illustration, the control theory is applied to the vibration of the hydrogen fluoride molecule embedded in a non-Markovian dissipative medium. The importance of control-dissipation correlation is evident in the results.     

The role of theory in the laboratory control of quantum dynamics phenomena

Interest in the control of quantum dynamics phenomena has grown in recent years, with laboratory studies showing increasing successes. The role of theory in the control of quantum phenomena encompasses the design of laser controls, the development of algorithms to guide the laboratory studies, and the means to analyze the ensuing dynamics observations. Laboratory laser control instrumentation has the special capability of performing massive numbers of experiments in a short period of time, to rapidly search for controls that meet the objectives. This unique laboratory feature needs to be factored in when considering how to best utilize theoretical analyses. The present paper reviews the role that theory is playing, as well as suggests some future avenues for theory in the laser control of quantum phenomena. Received: 8 June 2002 / Accepted: 7 October 2002 / Published online: 10 March 2003 Acknowledgements. The author acknowledges support from the National Science Fund and the US Department of Defense.     

Time-dependent quantum transport: An efficient method based on Liouville-von-Neumann equation for single-electron density matrix

Basing on our hierarchical equations of motion for time-dependent quantum transport [X. Zheng, G. H. Chen, Y. Mo, S. K. Koo, H. Tian, C. Y. Yam, and Y. J. Yan, J. Chem. Phys. 133, 114101 (2010)], we develop an efficient and accurate numerical algorithm to solve the Liouville-von-Neumann equation. We solve the real-time evolution of the reduced single-electron density matrix at the tight-binding level. Calculations are carried out to simulate the transient current through a linear chain of atoms, with each represented by a single orbital. The self-energy matrix is expanded in terms of multiple Lorentzian functions, and the Fermi distribution function is evaluated via the Pade? spectrum decomposition. This Lorentzian-Pade? decomposition scheme is employed to simulate the transient current. With sufficient Lorentzian functions used to fit the self-energy matrices, we show that the lead spectral function and the dynamics response can be treated accurately. Compared to the conventional master equation approaches, our method is much more efficient as the computational time scales cubically with the system size and linearly with the simulation time. As a result, the simulations of the transient currents through systems containing up to one hundred of atoms have been carried out. As density functional theory is also an effective one-particle theory, the Lorentzian-Pade? decomposition scheme developed here can be generalized for first-principles simulation of realistic systems.     

An efficient method for solving the quantum liouville equation: applications to electronic absorption spectroscopy

We examine a method for solving Liouville's equation, consisting of successive application of short time propagators which are evaluated by using fast Fourier transforms. The method is examined numerically by computing electronic absorption spectra. The procedure is very efficient when applied to the study of short time dynamics of systems whose quantum degrees of freedom are spatially localized.     

Basis set and method dependence in quantum theory of atoms in molecules calculations for covalent bonds

The influence of various small- and medium-size basis sets used in Hartree-Fock (HF) and density functional theory (DFT)/B3LYP calculations on results of quantum theory of atoms in molecules based (QTAIM-based) analysis of bond parameters is investigated for several single, double, and triple covalent bonds. It is shown that, in general, HF and DFT/B3LYP methods give very similar QTAIM results with respect to the basis set. The smallest 6-31G basis set and DZ-quality basis sets of Dunning type lead to poor results in comparison to those obtained by the most reliable aug-cc-pVTZ. On the contrary, 6-311++G(2df,2pd) and in a somewhat lesser extent 6-311++G(3df,3pd) basis sets give satisfactory values of QTAIM parameters. It is also demonstrated that QTAIM calculations may be sensitive for the method and basis set in the case of multiple and more polarized bonds.     

Computational method for the retarded potential in the real‐time simulation of quantum electrodynamics

We discuss the method to compute the integrals, which appear in the retarded potential term for a real‐time simulation based on quantum electrodynamics. We show that the oscillatory integrals over the infinite interval involved in them can be efficiently performed by the method developed by Ooura and Mori based on the double exponential formula. © 2016 Wiley Periodicals, Inc.     

Optimum and efficient sampling for variational quantum Monte Carlo

Quantum mechanics for many-body systems may be reduced to the evaluation of integrals in 3N dimensions using Monte Carlo, providing the Quantum Monte Carlo ab initio methods. Here we limit ourselves to expectation values for trial wave functions, that is to variational quantum Monte Carlo. Almost all previous implementations employ samples distributed as the physical probability density of the trial wave function, and assume the central limit theorem to be valid. In this paper we provide an analysis of random error in estimation and optimization that leads naturally to new sampling strategies with improved computational and statistical properties. A rigorous lower limit to the random error is derived, and an efficient sampling strategy presented that significantly increases computational efficiency. In addition the infinite variance heavy tailed random errors of optimum parameters in conventional methods are replaced with a Normal random error, strengthening the theoretical basis of optimization. The method is applied to a number of first row systems and compared with previously published results.     

The spin-density-functional formalism for quantum mechanical calculations: Test on diatomic molecules with an efficient numerical method

We have applied the spin-density-functional (SDF ) formalism with the local-spin-density (LSD ) approximation to a number of small molecules with the primary aim of testing the approximation for molecular applications. A new numerical method to solve the one-electron wave equation is developed, utilizing the special features of the SDF formalism. We have calculated energy curves, dissociation energies, and equilibrium distances for some diatomic molecules [H (²Σ, ²Σ), H₂(¹Σ, ³Σ), He (¹Σ), and He₂(¹Σ)] and the vibrational frequencies of H₂. The deviations from the experimental results are typically 1/2 eV for the energies and ≤ 0.1 Å for the distances. We discuss the LSD approximation using the concept of an exchange-correlation hole and make predictions about the applicability to other molecules. The LSD approximation is compared with the Hartree-Fock and multiple-scattering-Xα methods and some difficulties in the latter methods are pointed out. It is argued that the SDF formalism within the LSD approximation has physical advantages compared to the Hartree-Fock and Xα methods and that it should provide a simple and useful method for a broad range of applications.