Multilayer Multiconfiguration Time-dependent Hartree Method Research Articles

A tensor network view of multilayer multiconfiguration time-dependent Hartree methods

The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method and the density matrix renormalisation group (DMRG) are powerful workhorses applied mostly in different scientific fields. Although both methods are based on tensor network states, very different mathematical languages are used for describing them. This severely limits knowledge transfer and sometimes leads to re-inventions of ideas well known in the other field. Here, we review ML-MCTDH and DMRG theory using both MCTDH expressions and tensor network diagrams. We derive the ML-MCTDH equations of motions using diagrams and compare them with time-dependent and time-independent DMRG algorithms. We further review two selected recent advancements. The first advancement is related to optimising unoccupied single-particle functions in MCTDH, which corresponds to subspace enrichment in the DMRG. The second advancement is related to finding optimal tree structures and on highlighting similarities and differences of tensor networks used in MCTDH and DMRG theories. We hope that this contribution will foster more fruitful cross-fertilisation of ideas between ML-MCTDH and DMRG.

Compact sum-of-products form of the molecular electronic Hamiltonian based on canonical polyadic decomposition.

We propose an approach to represent the second-quantized electronic Hamiltonian in a compact sum-of-products (SOP) form. The approach is based on the canonical polyadic decomposition of the original Hamiltonian projected onto the sub-Fock spaces formed by groups of spin-orbitals. The algorithm for obtaining the canonical polyadic form starts from an exact sum-of-products, which is then optimally compactified using an alternating least squares procedure. We discuss the relation of this specific SOP with related forms, namely the Tucker format and the matrix product operator often used in conjunction with matrix product states. We benchmark the method on the electronic dynamics of an excited water molecule, trans-polyenes, and the charge migration in glycine upon inner-valence ionization. The quantum dynamics are performed with the multilayer multiconfiguration time-dependent Hartree method in second quantization representation. Other methods based on tree-tensor Ansätze may profit from this general approach.

Coherent Transient Localization Mechanism of Interchain Exciton Transport in Regioregular P3HT: A Quantum-Dynamical Study.

Transient localization has been proposed as a transport mechanism in organic materials, for both charge carriers and excitons. Here, we characterize a quantum coherent transient localization mechanism using full quantum simulations of an H-aggregated model system representative of regioregular poly(3-hexylthiophene) (rrP3HT). A Frenkel-Holstein Hamiltonian parametrized from first principles is considered, including local high-frequency modes and anharmonic, site-correlated interchain modes. Quantum-dynamical calculations are carried out using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method for a 13-site system with 195 vibrational modes, under periodic boundary conditions. It is shown that temporary localization of exciton polarons alternates with resonant transfer driven by interchain modes. While the transport process is mainly determined by exciton-polarons at the low-energy band edge, persistent coupling with the excitonic manifold is observed, giving rise to a nonadiabatic excitonic flux. This elementary transport mechanism remains preserved for limited static disorder and gives way to Anderson localization when the static disorder becomes dominant.

Quantum and classical molecular dynamics for H atom scattering from graphene.

This work presents systematic comparisons between classical molecular dynamics (cMD) and quantum dynamics (QD) simulations of 15-dimensional and 75-dimensional models in their description of H atom scattering from graphene. We use an experimentally validated full-dimensional neural network potential energy surface of a hydrogen atom interacting with a large cell of graphene containing 24 carbon atoms. For quantum dynamics simulations, we apply Monte Carlo canonical polyadic decomposition to transform the original potential energy surface (PES) into a sum of products form and use the multi-layer multi-configuration time-dependent Hartree method to simulate the quantum scattering of a hydrogen or deuterium atom with an initial kinetic energy of 1.96 or 0.96 eV and an incident angle of 0°, i.e., perpendicular to the graphene surface. The cMD and QD initial conditions have been carefully chosen in order to be as close as possible. Our results show little differences between cMD and QD simulations when the incident energy of the H atom is equal to 1.96 eV. However, a large difference in sticking probability is observed when the incident energy of the H atom is equal to 0.96 eV, indicating the predominance of quantum effects. To the best of our knowledge, our work provides the first benchmark of quantum against classical simulations for a system of this size with a realistic PES. Additionally, new projectors are implemented in the Heidelberg multi-configuration time-dependent Hartree package for the calculation of the atom scattering energy transfer distribution as a function of outgoing angles.

Interaction-controlled impurity transport in trapped mixtures of ultracold bosons

We explore the dynamical transport of an impurity between different embedding majority species which are spatially separated in a double well. The transfer and storage of the impurity is triggered by dynamically changing the interaction strengths between the impurity and the two majority species. We find a simple but efficient protocol consisting of linear ramps of majority-impurity interactions at designated times to pin or unpin the impurity. Our study of this highly imbalanced few-body triple mixture is conducted with the multi-layer multi-configuration time-dependent Hartree method for atomic mixtures which accounts for all interaction-induced correlations. We analyze the dynamics in terms of single-particle densities, entanglement growth and provide an effective potential description involving mean-fields of the interacting components. The majority components remain self-trapped in their individual wells at all times, which is a crucial element for the effectiveness of our protocol. During storage times each component performs low-amplitude dipole oscillations in a single well. Unexpectedly, the inter-species correlations possess a stabilizing impact on the transport and storage properties of the impurity particle.

Quantum dynamical study of inter-chain exciton transport in a regioregular P3HT model system at finite temperature: HJ vs H-aggregate models.

We report on quantum dynamical simulations of inter-chain exciton transport in a model of regioregular poly(3-hexylthiophene), rr-P3HT, at finite temperature using the Multi-Layer Multi-Configuration Time-Dependent Hartree method for a system of up to 63 electronic states and 180 vibrational modes. A Frenkel Hamiltonian of HJ aggregate type is used along with a reduced H-aggregate representation; electron-phonon coupling includes local high-frequency modes as well as anharmonic intermolecular modes. The latter are operative in mediating inter-chain transport by a mechanism of transient localization type. Strikingly, this mechanism is found to be of quantum coherent character and involves non-adiabatic effects. Using periodic boundary conditions, a normal diffusion regime is identified from the exciton mean-squared displacement, apart from early-time transients. Diffusion coefficients are found to be of the order of 3 × 10-3cm2/s, showing a non-linear increase with temperature.

Multilayer Multiconfiguration Time-Dependent Hartree Study on the Mode-/Bond-Specific Quantum Dynamics of Water Dissociation on Cu(111).

In this work, full-dimensional (9D) quantum dynamics calculations on mode-/bond-specific surface scattering of a water molecule on a copper (111) rigid surface are performed through the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method. To easily perform the ML-MCTDH calculations on such a triatomic molecule-surface system, we first choose specific Jacobi coordinates as a set of coordinates of water. Next, to efficiently perform the 9D ML-MCTDH wavepacket propagation, the potential energy surface is transferred to a canonical polyadic decomposition form with the aid of a Monte Carlo-based method. Excitation-specific dissociation probabilities of H2O on Cu(111) are computed, and mode-/bond-specific dynamics are demonstrated by comparison with a probability curve computed for a water molecule in the ground state. The dependence of the dissociation probability of the initial state of H2O is studied, and it is found that the excitation-specific dissociation probabilities can be divided into three groups. We find that the vibrationally excited states enhance the dissociation reactivity of H2O, while the rotationally excited states hardly influence it.

Artificial atoms from cold bosons in one dimension

We investigate the ground-state properties of weakly repulsive one-dimensional bosons in the presence of an attractive zero-range impurity potential. First, we derive mean-field solutions to the problem on a finite ring for the two asymptotic cases: (i) all bosons are bound to the impurity and (ii) all bosons are in a scattering state. Moreover, we derive the critical line that separates these regimes in the parameter space. In the thermodynamic limit, this critical line determines the maximum number of bosons that can be bound by the impurity potential, forming an artificial atom. Second, we validate the mean-field results using the flow equation approach and the multi-layer multi-configuration time-dependent Hartree method for atomic mixtures. While beyond-mean-field effects destroy long-range order in the Bose gas, the critical boson number is unaffected. Our findings are important for understanding such artificial atoms in low-density Bose gases with static and mobile impurities.

Breathing dynamics of the few-body Bose polaron in a species-selective harmonic trap

We perform an extensive numerical study on the breathing dynamics of a few-body Bose polaron setup in a one-dimensional species-selective harmonic trap. The dynamics is triggered by a quench of the impurity trap. The excitation of the background majority atoms is mediated via the majority-impurity interaction. The breathing spectrum is obtained for different numbers of majority particles, several values of the majority-component interaction strengths and trap ratios. It is further compared to the breathing spectrum of a particle-balanced few-body Bose-Bose mixture. In particular, for equal post-quench traps the employed protocol allows to couple states of different center-of-mass parity in contrast to species-symmetric trap quenches. Among the participating eigenstates we identify one having odd center-of-mass parity and even global parity. The breathing frequency induced by this state is a monotonically decreasing function of the coupling parameter. Importantly, in order to be observable it requires the entanglement between the species to be taken into account. We demonstrate this by comparing the numerically exact results obtained by means of the Multi-Layer Multi-Configuration Time-Dependent Hartree Method for Mixtures to the ones of a species mean-field ansatz. The entanglement-sensitive breathing frequency persists also for unequal post-quench traps where the center-of-mass cannot be decoupled. Finally, we analyze the impact of parity symmetry on the breathing dynamics by initializing a state of odd global parity. We evidence a striking resemblance to the ground state breathing dynamics.

Quantum Dynamics of Electron–Hole Separation in Stacked Perylene Diimide-Based Self-Assembled Nanostructures

We report on high-dimensional quantum dynamical simulations of electron–hole separation in self-assembled mesomorphic nanostructures composed of donor–acceptor conjugated co-oligomers. The latter are based on perylene diimide (PDI) acceptor units combined with fluorene-thiophene-benzothiadiazole donor units, which form highly ordered, stacked structural motifs upon self-assembly. Simulations are shown for a first-principles parametrized model lattice of 25 stacked PDI units under the effects of an applied external field and temperature. The simulations are carried out with the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method with nearly 900 vibrational degrees of freedom and 25 electronic states. Temperature effects are included using the thermofield dynamics approach. A transition between a short-time coherent dynamics and a kinetic regime is highlighted. From a flux-over-population analysis, electron–hole dissociation rates are obtained in the range of 5–20 ns–1 in the absence of static disorder, exhibiting a moderate field and temperature dependence. These results for electron–hole separation rates can be employed as a benchmark to calibrate the parametrization of kinetic Monte Carlo simulations applied to much larger lattice sizes.

Comparison of the multi-layer multi-configuration time-dependent Hartree (ML-MCTDH) method and the density matrix renormalization group (DMRG) for ground state properties of linear rotor chains.

We demonstrate the applicability of the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method to the problem of computing ground states of one-dimensional chains of linear rotors with dipolar interactions. Specifically, we successfully obtain energies, entanglement entropies, and orientational correlations that are in agreement with the Density Matrix Renormalization Group (DMRG), which has been previously used for this system. We find that the entropies calculated by ML-MCTDH for larger system sizes contain nonmonotonicity, as expected in the vicinity of a second-order quantum phase transition between ordered and disordered rotor states. We observe that this effect remains when all couplings besides nearest-neighbor are omitted from the Hamiltonian, which suggests that it is not sensitive to the rate of decay of the interactions. In contrast to DMRG, which is tailored to the one-dimensional case, ML-MCTDH (as implemented in the Heidelberg MCTDH package) requires more computational time and memory, although the requirements are still within reach of commodity hardware. The numerical convergence and computational demand of two practical implementations of ML-MCTDH and DMRG are presented in detail for various combinations of system parameters.

High-Dimensional Quantum Dynamics Study on Excitation-Specific Surface Scattering Including Lattice Effects of a Five-Atom Surface Cell.

In this work, high-dimensional (21D) quantum dynamics calculations on the mode-specific surface scattering of a carbon monoxide molecule on a copper(100) surface with lattice effects of a five-atom surface cell are performed through the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method. We employ a surface model in which five surface atoms near the impact site are treated as fully flexible quantum particles, while all other more distant atoms are kept at fixed locations. To efficiently perform the 21D ML-MCTDH wave packet propagation, the potential energy surface is transferred to a canonical polyadic decomposition form with the aid of a Monte Carlo-based method. Excitation-specific sticking probabilities of CO on Cu(100) are computed, and lattice effects caused by the flexible surface atoms are demonstrated by comparison with sticking probabilities computed for a rigid surface. The dependence of the sticking probability of the initial state of the system is studied, and it is found that the sticking probability is reduced when the surface atom on the impact site is initially vibrationally excited.

Multi-layer Gaussian-based multi-configuration time-dependent Hartree (ML-GMCTDH) simulations of ultrafast charge separation in a donor-acceptor complex.

We report on first applications of the Multi-Layer Gaussian-based Multi-Configuration Time-Dependent Hartree (ML-GMCTDH) method [Römer et al., J. Chem. Phys. 138, 064106 (2013)] beyond its basic two-layer variant. The ML-GMCTDH scheme provides an embedding of a variationally evolving Gaussian wavepacket basis into a hierarchical tensor representation of the wavefunction. A first-principles parameterized model Hamiltonian for ultrafast non-adiabatic dynamics in an oligothiophene-fullerene charge transfer complex is employed, relying on a two-state linear vibronic coupling model that combines a distribution of tuning type modes with an intermolecular coordinate that also modulates the electronic coupling. Efficient ML-GMCTDH simulations are carried out for up to 300 vibrational modes using an implementation within the QUANTICS program. Excellent agreement with reference ML-MCTDH calculations is obtained.

Spectral properties of a three-body atom-ion hybrid system

We consider a hybrid atom-ion system consisting of a pair of bosons interacting with a single ion in a quasi-one-dimensional trapping geometry. Building upon a model potential for the atom-ion interaction developed in earlier theoretical works, we investigate the behaviour of the low-energy eigenstates for varying contact interaction strength $g$ among the atoms. In particular, we contrast the two cases of a static and a mobile ion. Our study is carried out by means of the Multi-Layer Multi-Configuration Time-Dependent Hartree method for Bosons, a numerically-exact $\textit{ab initio}$ method for the efficient simulation of entangled mixtures. We find that repulsive atom interactions induce locally-distinct modifications of the atomic probability distribution unique to each eigenstate. Whilst the atoms on average separate from each other with increasing $g$, they do not necessarily separate from the ion. The mobility of the ion leads in general to greater separations among the atoms as well as between the atoms and the ion. Notably, we observe an exchange between the kinetic energy of the atoms and the atom-ion interaction energy for all eigenstates, which is both interaction- and mobility-induced. For the ground state, we provide an intuitive description by constructing an effective Hamiltonian for each species, which aptly captures the response of the atoms to the ion's mobility. Furthermore, the effective picture predicts enhanced localisation of the ion, in agreement with our results from exact numerical simulations.

Quantum dynamical simulations of intra-chain exciton diffusion in an oligo (para-phenylene vinylene) chain at finite temperature.

We report on quantum dynamical simulations of exciton diffusion in an oligo(para-phenylene vinylene) chain segment with 20 repeat units (OPV-20) at finite temperature, complementary to our recent study of the same system at T = 0 K [R. Binder and I. Burghardt, J. Chem. Phys. 152, 204120 (2020)]. Accurate quantum dynamical simulations are performed using the multi-layer multi-configuration time-dependent Hartree method as applied to a site-based Hamiltonian comprising 20 electronic states of Frenkel type and 460 vibrational modes, including site-local quinoid-distortion modes along with site-correlated bond-length alternation (BLA) modes, ring torsional modes, and an explicit harmonic-oscillator bath. A first-principles parameterized Frenkel-Holstein type Hamiltonian is employed, which accounts for correlations between the ring torsional modes and the anharmonically coupled BLA coordinates located at the same junction. Thermally induced fluctuations of the torsional modes are described by a stochastic mean-field approach, and their impact on the excitonic motion is characterized in terms of the exciton mean-squared displacement. A normal diffusion regime is observed under periodic boundary conditions, apart from transient localization features. Even though the polaronic exciton species are comparatively weakly bound, exciton diffusion is found to be a coherent-rather than hopping type-process, driven by the fluctuations of the soft torsional modes. Similar to the previous observations for oligothiophenes, the evolution for the most part exhibits a near-adiabatic dynamics of local exciton ground states (LEGSs) that adjust to the local conformational dynamics. However, a second mechanism, involving resonant transitions between neighboring LEGSs, gains importance at higher temperatures.

First-principles description of intra-chain exciton migration in an oligo(para-phenylene vinylene) chain. II. ML-MCTDH simulations of exciton dynamics at a torsional defect

The first-principles parameterized Frenkel-Holstein Hamiltonian developed in Paper I [R. Binder et al., J. Chem. Phys. 152, 204119 (2020)] is employed to carry out full quantum-dynamical simulations of an elementary exciton migration event in an oligo-(para-phenylene vinylene) chain with 20 repeat units (OPV-20). We consider a dynamic scenario where an initial torsional defect, creating a conjugation break, relaxes on a time scale of about 500 fs toward a planarized structure and triggers the spatial displacement of the photogenerated exciton. Accurate quantum dynamical simulations are performed using the multi-layer multi-configuration time-dependent Hartree method as applied to an OPV-20 system comprising 20 electronic states of Frenkel type and 60 vibrational modes. These include site-local quinoid-distortion modes, site-correlated bond-length alternation (BLA) modes, and an active ring torsional mode at the central junction. The simulations fully account for correlations between the ring torsional mode and the anharmonically coupled BLA coordinate located at the same junction. In accordance with our earlier studies of a related oligothiophene (OT) system [R. Binder, D. Lauvergnat, and I. Burghardt, Phys. Rev. Lett. 120, 227401 (2018)], these simulation results highlight that exciton migration is a coherent process driven by the fluctuations of "soft" modes, exemplified by the ring torsions. Conversely, these results also show that trapping due to high-frequency modes, leading to energetic stabilization of the exciton-polaron species, is weaker in OPV than in the OT system. This underscores not only the generic features of exciton dynamics in conjugated polymer systems, but also the role of molecular specificities.

Induced correlations between impurities in a one-dimensional quenched Bose gas

We explore the time evolution of two impurities in a trapped one-dimensional Bose gas that follows a change of the boson-impurity interaction. We study the induced impurity-impurity interactions and their effect on the quench dynamics. In particular, we report on the size of the impurity cloud, the impurity-impurity entanglement, and the impurity-impurity correlation function. The presented numerical simulations are based upon the variational multilayer multiconfiguration time-dependent Hartree method for bosons. To analyze and quantify induced impurity-impurity correlations, we employ an effective two-body Hamiltonian with a contact interaction. We show that the effective model consistent with the mean-field attraction of two heavy impurities explains qualitatively our results for weak interactions. Our findings suggest that the quench dynamics in cold-atom systems can be a tool for studying impurity-impurity correlations.

Computing vibrational eigenstates with tree tensor network states (TTNS).

We present how to compute vibrational eigenstates with tree tensor network states (TTNSs), the underlying ansatz behind the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method. The eigenstates are computed with an algorithm that is based on the density matrix renormalization group (DMRG). We apply this to compute the vibrational spectrum of acetonitrile (CH3CN) to high accuracy and compare TTNSs with matrix product states (MPSs), the ansatz behind the DMRG. The presented optimization scheme converges much faster than ML-MCTDH-based optimization. For this particular system, we found no major advantage of the more general TTNS over MPS. We highlight that for both TTNS and MPS, the usage of an adaptive bond dimension significantly reduces the amount of required parameters. We furthermore propose a procedure to find good trees.

Effective approach to impurity dynamics in one-dimensional trapped Bose gases

We investigate a temporal evolution of an impurity atom in a one-dimensional trapped Bose gas following a sudden change of the boson-impurity interaction strength. Our focus is on the effects of inhomogeneity due to the harmonic confinement. These effects can be described by an effective one-body model where both the mass and the spring constant are renormalized. This is in contrast to the classic renormalization, which addresses only the mass. We propose an effective single-particle Hamiltonian and apply the multilayer multiconfiguration time-dependent Hartree method for bosons to explore its validity. Numerical results suggest that the effective mass is smaller than the impurity mass, which means that it cannot straightforwardly be extracted from translationally invariant models.

Coherent Charge Transfer Exciton Formation in Regioregular P3HT: A Quantum Dynamical Study.

The ultrafast formation of charge transfer excitons (CTXs) in regioregular poly(3-hexyl thiophene) (rrP3HT) domains is elucidated by electronic structure and quantum dynamical studies of an aggregate model system comprising five stacked quaterthiophene units. Using a multistate vibronic coupling Hamiltonian parametrized by TDDFT calculations for 13 electronic states of Frenkel and CTX type, along with 78 vibrational modes, quantum dynamical simulations are carried out using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method. In line with time-resolved spectroscopic results [ De Sio , A. ; et al. Nat. Commun. 2016 , 7 , 13742 ], it is found that CTX formation occurs immediately upon photoexcitation, accompanied by sustained regular oscillations with a ∼22 fs periodicity. These coherent features, whose presence may seem surprising in a high-dimensional aggregate or thin film material, can be traced back to a dominant vibronic signature of CC stretch-type high-frequency modes. These vibrational signatures are found to be enhanced due to a collective vibronic response that is prompted by the initial generation of a delocalized bright exciton and its subsequent relaxation, by internal conversion, to a polaronic local exciton ground state.