Multi-configurational Time-dependent Hartree Approach Research Articles

QuTree: A tree tensor network package.

We present QuTree, a C++ library for tree tensor network approaches. QuTree provides class structures for tensors, tensor trees, and related linear algebra functions that facilitate the fast development of tree tensor network approaches such as the multilayer multiconfigurational time-dependent Hartree approach or the density matrix renormalization group approach and its various extensions. We investigate the efficiency of relevant tensor and tensor network operations and show that the overhead for managing the network structure is negligible, even in cases with a million leaves and small tensors. QuTree focuses on providing simple, high-level routines while retaining easy access to the backend to facilitate novel developments. We demonstrate the capabilities of the package by computing the eigenstates of coupled harmonic oscillator Hamiltonians and performing random circuit simulations on a virtual quantum computer.

Eigenstate calculation in the state-averaged (multi-layer) multi-configurational time-dependent Hartree approach.

A new approach for the calculation of eigenstates with the state-averaged (multi-layer) multi-configurational time-dependent Hartree (MCTDH) approach is presented. The approach is inspired by the recent work of Larsson [J. Chem. Phys. 151, 204102 (2019)]. It employs local optimization of the basis sets at each node of the multi-layer MCTDH tree and successive downward and upward sweeps to obtain a globally converged result. At the top node, the Hamiltonian represented in the basis of the single-particle functions (SPFs) of the first layer is diagonalized. Here p wavefunctions corresponding to the p lowest eigenvalues are computed by a block Lanczos approach. At all other nodes, a non-linear operator consisting of the respective mean-field Hamiltonian matrix and a projector onto the space spanned by the respective SPFs is considered. Here, the eigenstate corresponding to the lowest eigenvalue is computed using a short iterative Lanczos scheme. Two different examples are studied to illustrate the new approach: the calculation of the vibrational states of methyl and acetonitrile. The calculations for methyl employ the single-layer MCTDH approach, a general potential energy surface, and the correlation discrete variable representation. A five-layer MCTDH representation and a sum of product-type Hamiltonian are used in the acetonitrile calculations. Very fast convergence and order of magnitude reductions in the numerical effort compared to the previously used block relaxation scheme are found. Furthermore, a detailed comparison with the results of Avila and Carrington [J. Chem. Phys. 134, 054126 (2011)] for acetonitrile highlights the potential problems of convergence tests for high-dimensional systems.

Accurate Potential Energy Surfaces Using Atom-Centered Potentials and Minimal High-Level Data.

We demonstrate that a Δ-density functional theory (Δ-DFT) approach based on atom-centered potentials (ACPs) represents a computationally inexpensive and accurate method for representing potential energy surfaces (PESs) for the HONO and HFCO molecules and vibrational frequencies derived therefrom. Using as few as 100 CCSD(T)-F12a reference energies, ACPs developed for use with B3LYP/def2-TZVPP are shown to produce PESs for HONO and HFCO with mean absolute errors of 27.7 and 5.8 cm-1, respectively. Application of the multiconfigurational time-dependent Hartree (MCTDH) method with ACP-corrected B3LYP/def2-TZVPP PESs produces vibrational frequencies for cis- and trans-HONO with mean absolute percent errors (MAPEs) of 0.8 and 1.1, compared to 0.8 obtained for the two isomers with CCSD(T)-F12a/cc-pVTZ-F12/MCTDH. For HFCO, the vibrational frequencies obtained using the present (Δ-DFT)/MCTDH approach give a MAPE of 0.1, which is the error obtained with CCSD(T)-F12a/cc-pVTZ-F12/MCTDH. The ACP approach is therefore successful in representing a PES calculated at a high level of theory (CCSD(T)-F12a) and a promising method for the development of a general protocol for the representation of accurate molecular PESs and the calculation of molecular properties from them.

Stochastic multi-configuration time-dependent Hartree for dissipative quantum dynamics with strong intramolecular coupling.

In this article, we explore the dissipation dynamics of a strongly coupled multidimensional system in contact with a Markovian bath, following a system-bath approach. We use in this endeavor the recently developed stochastic multi-configuration time-dependent Hartree approach within the Monte Carlo wave packet formalism [S. Mandal et al., J. Chem. Phys. 156, 094109 (2022)]. The method proved to yield thermalized ensembles of wave packets when intramolecular coupling is weak. To treat strongly coupled systems, new Lindblad dissipative operators are constructed as linear combinations of the system coordinates and associated momenta. These are obtained by a unitary transformation to a normal mode representation, which reduces intermode coupling up to second order. Additionally, we use combinations of generalized raising/lowering operators to enforce the Boltzmann distribution in the dissipation operators, which yield perfect thermalization in the harmonic limit. The two ansatz are tested using a model two-dimensional Hamiltonian, parameterized to disentangle the effects of intramolecular potential coupling, of strong mode mixing observed in Fermi resonances, and of anharmonicity.

Exciton Dissociation in a Model Organic Interface: Excitonic State-Based Surface Hopping versus Multiconfigurational Time-Dependent Hartree.

Quantum dynamical simulations are essential for a molecular-level understanding of light-induced processes in optoelectronic materials, but they tend to be computationally demanding. We introduce an efficient mixed quantum-classical nonadiabatic molecular dynamics method termed eXcitonic state-based Surface Hopping (X-SH), which propagates the electronic Schrödinger equation in the space of local excitonic and charge-transfer electronic states, coupled to the thermal motion of the nuclear degrees of freedom. The method is applied to exciton decay in a 1D model of a fullerene–oligothiophene junction, and the results are compared to the ones from a fully quantum dynamical treatment at the level of the Multilayer Multiconfigurational Time-Dependent Hartree (ML-MCTDH) approach. Both methods predict that charge-separated states are formed on the 10–100 fs time scale via multiple “hot-exciton dissociation” pathways. The results demonstrate that X-SH is a promising tool advancing the simulation of photoexcited processes from the molecular to the true nanomaterials scale.

Non-Markovian vibrational relaxation dynamics at surfaces.

Vibrational dynamics of adsorbates near surfaces plays both an important role for applied surface science and as a model lab for studying fundamental problems of open quantum systems. We employ a previously developed model for the relaxation of a D-Si-Si bending mode at a D:Si(100)-(2 × 1) surface, induced by a "bath" of more than 2000 phonon modes [Lorenz and P. Saalfrank, Chem. Phys. 482, 69 (2017)], to extend previous work along various directions. First, we use a Hierarchical Effective Mode (HEM) model [Fischer et al., J. Chem. Phys. 153, 064704 (2020)] to study relaxation of higher excited vibrational states than hitherto done by solving a high-dimensional system-bath time-dependent Schrödinger equation (TDSE). In the HEM approach, (many) real bath modes are replaced by (much less) effective bath modes. Accordingly, we are able to examine scaling laws for vibrational relaxation lifetimes for a realistic surface science problem. Second, we compare the performance of the multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) approach with that of the recently developed coherent-state-based multi-Davydov-D2 Ansatz [Zhou et al., J. Chem. Phys. 143, 014113 (2015)]. Both approaches work well, with some computational advantages for the latter in the presented context. Third, we apply open-system density matrix theory in comparison with basically "exact" solutions of the multi-mode TDSEs. Specifically, we use an open-system Liouville-von Neumann (LvN) equation treating vibration-phonon coupling as Markovian dissipation in Lindblad form to quantify effects beyond the Born-Markov approximation.

Spin-vibronic coupling in the quantum dynamics of a Fe(III) trigonal-bipyramidal complex.

The presence of a high density of excited electronic states in the immediate vicinity of the optically bright state of a molecule paves the way for numerous photo-relaxation channels. In transition-metal complexes, the presence of heavy atoms results in a stronger spin-orbit coupling, which enables spin forbidden spin-crossover processes to compete with the spin-allowed internal conversion processes. However, no matter how effectively the states cross around the Franck-Condon region, the degree of vibronic coupling, of both relativistic and non-relativistic nature, drives the population distribution among these states. One such case is demonstrated in this work for the intermediate-spin Fe(III) trigonal-bipyramidal complex. A quantum dynamical investigation of the photo-deactivation mechanism in the Fe(III) system is presented using the multi-configurational time-dependent Hartree approach based on the vibronic Hamiltonian whose coupling terms are derived from the state-averaged complete active space self-consistent field/complete active space with second-order perturbation theory (CASPT2) calculations and spin-orbit coupling of the scalar-relativistic CASPT2 states. The results of this study show that the presence of a strong (non-relativistic) vibronic coupling between the optically bright intermediate-spin state and other low-lying states of the same spin-multiplicity overpowers the spin-orbit coupling between the intermediate-spin and high-spin states, thereby lowering the chances of spin-crossover while exhibiting ultrafast relaxation among the intermediate-spin states. In a special case, where the population transfer pathway via the non-relativistic vibronic coupling is blocked, the probability of the spin-crossover is found to increase. This suggests that a careful modification of the complex by incorporation of heavier atoms with stronger relativistic effects can enhance the spin-crossover potential of Fe(III) intermediate-spin complexes.

The multi-configurational time-dependent Hartree approach in optimized second quantization: Thermal ensembles and statistical sampling

The recently introduced multi-layer (ML) multi-configurational time-dependent Hartree (MCTDH) in optimized second quantization representation (oSQR) approach combines the use of an optimized time-dependent orbital basis and the multi-layer MCTDH tensor contraction scheme to efficiently describe the quantum dynamics of system consisting of identical particles. Extending the original work on the subject, which studied propagation in real and imaginary time for Hamiltonians with flexible and fixed particle numbers, here the representation of thermal ensembles and the calculation of thermally averaged observables within the ML-MCTDH-oSQR is investigated. Different statistal sampling schemes for fixed and flexible particle numbers are introduced and analyzed. Numerical calculations studying a Hubbard model are used to illustrate the properties of the different schemes.

Time evolution of ML-MCTDH wavefunctions. II. Application of the projector splitting integrator.

The multi-layer multi-configuration time-dependent Hartree (ML-MCTDH) approach can suffer from numerical instabilities whenever the wavefunction is weakly entangled. These instabilities arise from singularities in the equations of motion (EOMs) and necessitate the use of regularization of the EOMs. The Projector Splitting Integrator (PSI) has previously been presented as an approach for evolving ML-MCTDH wavefunctions that is free of singularities. Here, we will discuss the implementation of the multi-layer PSI with a particular focus on how the steps required relate to those required to implement standard ML-MCTDH. We demonstrate the efficiency and stability of the PSI for large ML-MCTDH wavefunctions containing up to hundreds of thousands of nodes by considering a series of spin-boson models with up to 106 bath modes and find that for these problems, the PSI requires roughly 3-4 orders of magnitude fewer Hamiltonian evaluations and 2-3 orders of magnitude fewer Hamiltonian applications than standard ML-MCTDH and 2-3/1-2 orders of magnitude fewer evaluations/applications than approaches that use improved regularization schemes. Finally, we consider a series of significantly more challenging multi-spin-boson models that require much larger numbers of single-particle functions with wavefunctions containing up to ∼1.3×109 parameters to obtain accurate dynamics.

A thermofield-based multilayer multiconfigurational time-dependent Hartree approach to non-adiabatic quantum dynamics at finite temperature.

We introduce a thermofield-based formulation of the multilayer multiconfigurational time-dependent Hartree (MCTDH) method to study finite temperature effects on non-adiabatic quantum dynamics from a non-stochastic, wave function perspective. Our approach is based on the formal equivalence of bosonic many-body theory at zero temperature with a doubled number of degrees of freedom and the thermal quasi-particle representation of bosonic thermofield dynamics (TFD). This equivalence allows for a transfer of bosonic many-body MCTDH as introduced by Wang and Thoss to the finite temperature framework of thermal quasi-particle TFD. As an application, we study temperature effects on the ultrafast internal conversion dynamics in pyrazine. We show that finite temperature effects can be efficiently accounted for in the construction of multilayer expansions of thermofield states in the framework presented herein. Furthermore, we find our results to agree well with existing studies on the pyrazine model based on the ρMCTDH method.

Benchmarking the multiconfigurational Hartree method by the exact wavefunction of two harmonically trapped bosons with contact interaction

We consider two bosons in a one-dimensional harmonic trap, interacting by a contact potential, and compare the exact solution of this problem to a self-consistent numerical solution by using the multiconfigurational time-dependent Hartree (MCTDH) method. We thereby benchmark the predictions of the MCTDH method with a few-body problem that has an analytical solution for the most commonly experimentally realized interaction potential in ultracold quantum gases. It is found that exact ground state energy and first order correlations are accurately reproduced by MCTDH up to the intermediate dimensionless coupling strengths corresponding to typical background scattering lengths of magnetically trapped ultracold dilute Bose gases. For larger couplings, established for example by (a combination of) Feshbach resonances and optical trapping, the MCTDH approach overestimates the depth of the trap-induced correlation dip of first order correlations in position space, as well as overestimates the fragmentation, defined as the average relative occupation of orbitals other than the energetically lowest one. We anticipate that qualitatively similar features in the correlation function may arise for larger particle numbers, paving the way for a quantitative assessment of the accuracy of MCTDH by experiments with ultracold atoms.

Encapsulation of a Water Molecule inside C60 Fullerene: The Impact of Confinement on Quantum Features

We introduce an efficient quantum fully coupled computational scheme within the multiconfiguration time-dependent Hartree (MCTDH) approach to handle the otherwise extremely costly computations of translational–rotational–vibrational states and energies of light-molecule endofullenes. Quantum calculations on energy levels are reported for a water molecule inside C60 fullerene by means of such a systematic approach that includes all nine degrees of freedom of H2O@C60 and does not consider restrictions above them. The potential energy operator is represented as a sum of natural potentials employing the n-mode expansion, along with the exact kinetic energy operator, by introducing a set of Radau internal coordinates for the H2O molecule. On the basis of the present rigorous computations, various aspects of the quantized intermolecular dynamics upon confinement of H2O@C60 are discussed, such as the rotational energy level splitting and the significant frequency shifts of the encapsulated water molecule vibrations. The impact of water encapsulation on quantum features is explored, and insights into the nature of the underlying forces are provided, highlighting the importance of a reliable first-principles description of the guest–host interactions.

A rectangular collocation multi-configuration time-dependent Hartree (MCTDH) approach with time-independent points for calculations on general potential energy surfaces.

We introduce a collocation-based multi-configuration time-dependent Hartree (MCTDH) method that uses more collocation points than basis functions. We call it the rectangular collocation MCTDH (RC-MCTDH) method. It does not require that the potential be a sum of products. RC-MCTDH has the important advantage that it makes it simple to use time-independent collocation points. When using time-independent points, it is necessary to evaluate the potential energy function only once and not repeatedly during an MCTDH calculation. It is inexpensive and straightforward to use RC-MCTDH with combined modes. Using more collocation points than basis functions enables one to reduce errors in energy levels without increasing the size of the single-particle function basis. On the contrary, whenever a discrete variable representation is used, the only way to reduce the quadrature error is to increase the basis size, which then also reduces the basis-set error. We demonstrate that with RC-MCTDH and time-independent points, it is possible to calculate accurate eigenenergies of CH3 and CH4.

Direct product-type grid representations for angular coordinates in extended space and their application in the MCTDH approach.

Multi-configurational time-dependent Hartree (MCTDH) calculations using time-dependent grid representations can be used to accurately simulate high-dimensional quantum dynamics on general ab initio potential energy surfaces. Employing the correlation discrete variable representation, sets of direct product type grids are employed in the calculation of the required potential energy matrix elements. This direct product structure can be a problem if the coordinate system includes polar and azimuthal angles that result in singularities in the kinetic energy operator. In the present work, a new direct product-type discrete variable representation (DVR) for arbitrary sets of polar and azimuthal angles is introduced. It employs an extended coordinate space where the range of the polar angles is taken to be [-π, π]. The resulting extended space DVR resolves problems caused by the singularities in the kinetic energy operator without generating a very large spectral width. MCTDH calculations studying the F·CH4 complex are used to investigate important properties of the new scheme. The scheme is found to allow for more efficient integration of the equations of motion compared to the previously employed cot-DVR approach [G. Schiffel and U. Manthe, Chem. Phys. 374, 118 (2010)] and decreases the required central processing unit times by about an order of magnitude.

The multi-configurational time-dependent Hartree approach in optimized second quantization: Imaginary time propagation and particle number conservation

The multilayer multiconfigurational time-dependent Hartree (MCTDH) in optimized second quantization representation (oSQR) approach combines the tensor contraction scheme of the multilayer MCTDH approach with the use of an optimized time-dependent orbital basis. Extending the original work on the subject [U. Manthe and T. Weike, J. Chem. Phys. 146, 064117 (2017)], here MCTDH-oSQR propagation in imaginary time and properties related to particle number conservation are studied. Differences between the orbital equation of motion in real and imaginary time are highlighted and a new gauge operator, which facilitates efficient imaginary time propagation, is introduced. Studying Bose-Hubbard models, particle number conservation in MCTDH-oSQR calculations is investigated in detail. Interesting properties of the single-particle functions used in the multilayer MCTDH representation are identified. Based on these results, a tensor contraction scheme, which explicitly utilizes particle number conservation, is suggested.

Dissociative Electron Attachment to MgCN

SynopsisDissociative electron attachment (DEA) to the molecule MgCN and its isomer MgNC have been proposed as possible sources of CN− in the interstellar media. We have carried out electron scattering calculations using the Complex Kohn Variational Method as a function of the internal degrees of freedom to obtain the resonance energy surfaces and autoionization widths. We use this data as input to form the Hamiltonian relevant to the nuclear dynamics. The multidimensional wave equation is solved using the MultiConfiguration Time-Dependent Hartree (MCTDH) approach. We compute the DEA cross sections.

Dissociative electron attachment to MgCN

Dissociative electron attachment (DEA) to the molecule MgCN and its isomer MgNC has been proposed as a possible source of CN− in the interstellar media. We have carried out electron scattering calculations using the complex Kohn Variational Method as a function of the internal degrees of freedom of the molecule to obtain the resonance energy surfaces and autoionization widths. We use these data as input to form the Hamiltonian relevant to the nuclear dynamics. The multidimensional time-dependent Schrodinger equation is solved using the MultiConfiguration Time-Dependent Hartree (MCTDH) approach. We compute the DEA cross sections and discuss the implications for CN− formation in circumstellar envelopes.

Vibronic coupling in the F·CH4 prereactive complex

The F + CH4 → HF + CH3 reaction shows a counter-intuitive mode-selective chemistry and prominent resonances. The prereactive F·CH4 complex formed in the entrance channel is assumed to play an important role in the dynamics of the reaction. The present work investigates the effect of nonadiabatic transitions and the geometric phase on the low-lying quasibound states of the F·CH4 complex. Quantum dynamics calculations employing the multiconfigurational time-dependent Hartree approach and accurately accounting for vibronic as well as spin-orbit coupling are performed. Extending previous work [D. Schäpers and U. Manthe, J. Phys. Chem. A 120, 3186 (2016)], which was restricted to the dynamics on a single adiabatic potential energy surface and found the relative rotation of F and CH4 to proceed almost freely, we found chaotic patterns if vibronic coupling is included. While nonadiabatic transitions strongly affect individual resonances, their effect on averaged quantum state densities and the photodetachment spectrum of F⋅CH4 - is found to be minor.

Nonequilibrium heat transport in a molecular junction: A mixed quantum-classical approach.

In a recent study [J. Liu et al., J. Chem. Phys. 149, 224104 (2018)], we developed a general mixed quantum-classical framework for studying heat transport through molecular junctions, in which the junction molecule is treated quantum mechanically and the thermal reservoirs to which the molecule is coupled are treated classically. This framework yields expressions for the transferred heat and steady-state heat current, which could be calculated using a variety of mixed quantum-classical dynamics methods. In this work, we use the recently developed "Deterministic Evolution of Coordinates with Initial Decoupled Equations" (DECIDE) method for calculating the steady-state heat current in the nonequilibrium spin-boson model in a variety of parameter regimes. Our results are compared and contrasted with those obtained using the numerically exact multilayer multiconfiguration time-dependent Hartree approach, and using approximate methods, including mean field theory, Redfield theory, and adiabatic mixed quantum-classical dynamics. Despite some quantitative differences, the DECIDE method performs quite well, is capable of capturing the expected trends in the steady-state heat current, and, overall, outperforms the approximate methods. These results hold promise for DECIDE simulations of nonequilibrium heat transport in realistic models of nanoscale systems.

A pruned collocation-based multiconfiguration time-dependent Hartree approach using a Smolyak grid for solving the Schrödinger equation with a general potential energy surface.

Standard multiconfiguration time-dependent Hartree (MCTDH) calculations use a direct product basis and rely on the potential being a sum of products (SOPs). The size of the direct product MCTDH basis scales exponentially with the number of atoms. Accurate potentials may not be SOPs. We introduce an MCTDH approach that uses a pruned basis and a collocation grid. Pruning the basis significantly reduces its size. Collocation makes it possible to do calculations using a potential that is not a SOP. The collocation point set is a Smolyak grid. Strategies using pruned MCTDH bases already exist, but they work only if the potential is a SOP. Strategies for using MCTDH with collocation also exist, but they work only if the MCTDH basis is a direct product. In this paper, we combine a pruned basis with collocation. This makes it possible to mitigate the direct-product basis size problem and do calculations when the potential is not a SOP. Because collocation is used, there are no integrals and no need for quadrature. All required matrix-vector products can be evaluated sequentially. We use nested sets of collocation points and hierarchical basis functions. They permit efficient inversion of the (large) matrix whose elements are basis functions evaluated at points, which is necessary to transform values of functions at points to basis coefficients. The inversion technique could be used outside of chemical physics. We confirm the validity of this new pruned, collocation-based (PC-)MCTDH approach by calculating the first 50 vibrational eigenenergies of CH2NH.