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Quantum dynamics simulation and computational spectroscopy serve as indispensable tools for the theoretical understanding of various fundamental physical and chemical processes, ranging from charge transfer to photochemical reactions. When simulating realistic systems, the primary challenge stems from the overwhelming number of degrees of freedom and the pronounced many-body correlations. Here, we present Kylin-V, an innovative quantum dynamics package designed for accurate and efficient simulations of dynamics and spectroscopic properties of vibronic Hamiltonians for molecular systems and their aggregates. Kylin-V supports various quantum dynamics and computational spectroscopy methods, such as time-dependent density matrix renormalization group and our recently proposed single-site and hierarchical mapping approaches, as well as vibrational heat-bath configuration interaction. In this paper, we introduce the methodologies implemented in Kylin-V and illustrate their performances through a diverse collection of numerical examples. [ABSTRACT FROM AUTHOR]

Fewest-switches surface hopping (FSSH) has emerged as one of the leading methods for modeling the quantum dynamics of molecular systems. While its original formulation was limited to adiabatic populations, the growing interest in the application of FSSH to coherent phenomena prompts the question of how one should construct a complete density matrix based on FSSH trajectories. A straightforward solution is to define adiabatic coherences based on wavefunction coefficients. In this paper, we demonstrate that inconsistencies introduced in the density matrix through such treatment may lead to a violation of positivity. We furthermore show that a recently proposed coherent generalization of FSSH results in density matrices that satisfy positivity while yielding improved accuracy throughout much (but not all) of parameter space. [ABSTRACT FROM AUTHOR]

The generalized quantum master equation (GQME) provides a general and formally exact framework for simulating the reduced dynamics of open quantum systems. The recently introduced modified approach to the GQME (M-GQME) corresponds to a specific implementation of the GQME that is geared toward simulating the dynamics of the electronic reduced density matrix in systems governed by an excitonic Hamiltonian. Such a Hamiltonian, which is often used for describing energy and charge transfer dynamics in complex molecular systems, is given in terms of diabatic electronic states that are coupled to each other and correspond to different nuclear Hamiltonians. Within the M-GQME approach, the effect of the nuclear degrees of freedom on the time evolution of the electronic density matrix is fully captured by a memory kernel superoperator, which can be obtained from short-lived (compared to the time scale of energy/charge transfer) projection-free inputs. In this paper, we test the ability of the M-GQME to predict the energy transfer dynamics within a seven-state benchmark model of the Fenna–Matthews–Olson (FMO) complex, with the short-lived projection-free inputs obtained via the Ehrenfest method. The M-GQME with Ehrenfest-based inputs is shown to yield accurate results across a wide parameter range. It is also found to dramatically outperform the direct application of the Ehrenfest method and to provide better-behaved convergence with respect to memory time in comparison to an alternative implementation of the GQME approach previously applied to the same FMO model. [ABSTRACT FROM AUTHOR]

In this paper, we investigate the time evolution of quantum coherence—the off-diagonal elements of the density matrix of a multistate quantum system—from the perspective of the Wigner–Moyal formalism. This approach provides an exact phase space representation of quantum mechanics. We consider the coherent evolution of nuclear wavepackets in a molecule with two electronic states. For harmonic potentials, the problem is analytically soluble for both a fully quantum mechanical description and a semiclassical description. We highlight the serious deficiencies of the semiclassical treatment of coherence for general systems and illustrate how even qualitative accuracy requires higher order terms in the Moyal expansion to be included. The model provides an experimentally relevant example of a molecular Schrödinger's cat state. The alive and dead cats of the exact two-state quantum evolution collapse into a "zombie" cat in the semiclassical limit—an averaged behavior, neither alive nor dead, leading to significant errors. The inclusion of the Moyal correction restores a faithful simultaneously alive and dead representation of the cat that is experimentally observable. [ABSTRACT FROM AUTHOR]

The time dependent density matrix renormalization group (TD-DMRG) has become one of the cutting edge methods of quantum dynamics for complex systems. In this paper, we comparatively study the accuracy of three time evolution schemes in the TD-DMRG, the global propagation and compression method with the Runge-Kutta algorithm (P&C-RK), the time dependent variational principle based methods with the matrix unfolding algorithm (TDVP-MU), and with the projector-splitting algorithm (TDVP-PS), by performing benchmarks on the exciton dynamics of the Fenna-Matthews-Olson complex. We show that TDVP-MU and TDVP-PS yield the same result when the time step size is converged and they are more accurate than P&C-RK4, while TDVP-PS tolerates a larger time step size than TDVP-MU. We further adopt the graphical processing units to accelerate the heavy tensor contractions in the TD-DMRG, and it is able to speed up the TDVP-MU and TDVP-PS schemes by up to 73 times. [ABSTRACT FROM AUTHOR]

The molecular dynamics following the electronic B Π u 3 0 + ⟵ X Σ g + 1 photoexcitation of the iodine molecule embedded in solid krypton are studied quantum mechanically using the Gaussian variant of the multiconfigurational time-dependent Hartree method (G-MCTDH). The accuracy of the Gaussian wave packet approximation is validated against numerically exact MCTDH simulations for a fully anharmonic seven-dimensional model of the I2Kr18 cluster in a crystal Kr cage. The linear absorption spectrum, time-evolving vibrational probability densities, and I2 energy expectation value are accurately reproduced by the numerically efficient G-MCTDH approach. The reduced density matrix of the chromophore is analyzed in the coordinate, Wigner and energy representations, so as to obtain a multifaceted dynamical view of the guest-host interactions. Vibrational coherences extending over the bond distance range 2.7 Å < RI–I < 4.0 Å are found to survive for several vibrational periods, despite extensive dissipation. The present results prepare the ground for the simulation of time-resolved coherent Raman spectroscopy of the I2-krypton system addressed in Paper II. [ABSTRACT FROM AUTHOR]

We develop an accurate and numerically efficient non-adiabatic path-integral approach to simulate the non-linear spectroscopy of exciton–polariton systems. This approach is based on the partial linearized density matrix approach to model the exciton dynamics with explicit propagation of the phonon bath environment, combined with a stochastic Lindblad dynamics approach to model the cavity loss dynamics. Through simulating both linear and polariton two-dimensional electronic spectra, we systematically investigate how light–matter coupling strength and cavity loss rate influence the optical response signal. Our results confirm the polaron decoupling effect, which is the reduced exciton–phonon coupling among polariton states due to the strong light–matter interactions. We further demonstrate that the polariton coherence time can be significantly prolonged compared to the electronic coherence outside the cavity. [ABSTRACT FROM AUTHOR]

Kohn–Sham density functional theory calculations using conventional diagonalization based methods become increasingly expensive as temperature increases due to the need to compute increasing numbers of partially occupied states. We present a density matrix based method for Kohn–Sham calculations at high temperatures that eliminates the need for diagonalization entirely, thus reducing the cost of such calculations significantly. Specifically, we develop real-space expressions for the electron density, electronic free energy, Hellmann–Feynman forces, and Hellmann–Feynman stress tensor in terms of an orthonormal auxiliary orbital basis and its density kernel transform, the density kernel being the matrix representation of the density operator in the auxiliary basis. Using Chebyshev filtering to generate the auxiliary basis, we next develop an approach akin to Clenshaw–Curtis spectral quadrature to calculate the individual columns of the density kernel based on the Fermi operator expansion in Chebyshev polynomials and employ a similar approach to evaluate band structure and entropic energy components. We implement the proposed formulation in the SPARC electronic structure code, using which we show systematic convergence of the aforementioned quantities to exact diagonalization results, and obtain significant speedups relative to conventional diagonalization based methods. Finally, we employ the new method to compute the self-diffusion coefficient and viscosity of aluminum at 116 045 K from Kohn–Sham quantum molecular dynamics, where we find agreement with previous more approximate orbital-free density functional methods. [ABSTRACT FROM AUTHOR]

Tensor network decompositions of path integrals for simulating open quantum systems have recently been proven to be useful. However, these methods scale exponentially with the system size. This makes it challenging to simulate the non-equilibrium dynamics of extended quantum systems coupled with local dissipative environments. In this work, we extend the tensor network path integral (TNPI) framework to efficiently simulate such extended systems. The Feynman–Vernon influence functional is a popular approach used to account for the effect of environments on the dynamics of the system. In order to facilitate the incorporation of the influence functional into a multisite framework (MS-TNPI), we combine a matrix product state (MPS) decomposition of the reduced density tensor of the system along the sites with a corresponding tensor network representation of the time axis to construct an efficient 2D tensor network. The 2D MS-TNPI network, when contracted, yields the time-dependent reduced density tensor of the extended system as an MPS. The algorithm presented is independent of the system Hamiltonian. We outline an iteration scheme to take the simulation beyond the non-Markovian memory introduced by solvents. Applications to spin chains coupled to local harmonic baths are presented; we consider the Ising, XXZ, and Heisenberg models, demonstrating that the presence of local environments can often dissipate the entanglement between the sites. We discuss three factors causing the system to transition from a coherent oscillatory dynamics to a fully incoherent dynamics. The MS-TNPI method is useful for studying a variety of extended quantum systems coupled with solvents. [ABSTRACT FROM AUTHOR]

We introduce a practical method for compacting the time evolution of the quantum state of a closed physical system. The density matrix is specified as a function of a few time-independent observables where their coefficients are time-dependent. The key mathematical step is the vectorization of the surprisal, the logarithm of the density matrix, at each time point of interest. The time span used depends on the required spectral resolution. The entire course of the system evolution is represented as a matrix where each column is the vectorized surprisal at the given time point. Using the singular value decomposition (SVD) of this matrix, we generate realistic approximations for the time-independent observables and their respective time-dependent coefficients. This allows for a simplification of the algebraic procedure for determining the dominant constraints (the time-independent observables) in the sense of the maximal entropy approach. A non-stationary coherent initial state of a Morse oscillator is used to introduce the approach. We derive the analytical exact expression for the surprisal as a function of time, and this offers a benchmark for comparison with the accurate but approximate SVD results. We discuss two examples of a Morse potential of different anharmonicities, H2 and I2 molecules. We further demonstrate the approach for a two-coupled electronic state problem, the well-studied non-radiative decay of pyrazine from its bright state. Five constraints are found to be enough to capture the ultrafast electronic population exchange and to recover the dynamics of the wave packet in both electronic states. [ABSTRACT FROM AUTHOR]

This work explores the possibility of simulating an electron transfer process between a donor and an acceptor in real time using time-dependent density functional theory electron dynamics. To achieve this objective, a central issue to resolve is the definition of the initial state. This must be a non-equilibrium electronic state able to trigger the charge transfer dynamics; here, two schemes are proposed to prepare such states. One is based on the combination of the density matrices of the donor and acceptor converged separately with appropriate charges (for example, −1 for the donor and +1 for the acceptor). The second approach relied on constrained DFT to localize the charge on each fragment. With these schemes, electron transfer processes are simulated in different model systems of increasing complexity: an atomic hydrogen dimer, a polyacetylene chain, and the active site of the T. cruzi hybrid type A heme peroxidase, for which two possible electron transfer paths have been postulated. For the latter system, the present methodology applied in a hybrid Quantum Mechanics - Molecular Mechanics framework allows us to establish the relative probabilities of each path and provides insight into the inhibition of the electron transfer provoked by the substitution of tryptophan by phenylalanine in the W233F mutant. [ABSTRACT FROM AUTHOR]

Marcus theory has been successfully applied to molecular design for organic semiconductors with the aid of quantum chemistry calculations for the molecular parameters: the intermolecular electronic coupling V and the intramolecular charge reorganization energy λ. The assumption behind this is the localized nature of the electronic state for representing the charge carriers, being holes or electrons. As far as the quantitative description of carrier mobility is concerned, the direct application of Marcus semiclassical theory usually led to underestimation of the experimental data. A number of effects going beyond such a semiclassical description will be introduced here, including the quantum nuclear effect, dynamic disorder, and delocalization effects. The recently developed quantum dynamics simulation at the time-dependent density matrix renormalization group theory is briefly discussed. The latter was shown to be a quickly emerging efficient quantum dynamics method for the complex system. [ABSTRACT FROM AUTHOR]

The multiconfiguration time-dependent Hartree (MCTDH) method is a powerful method for solving the time-dependent Schrödinger equation in quantum molecular dynamics. It is, however, hampered by the so-called curse of dimensionality which results in exponential scaling with respect to the number of degrees of freedom in the system and, thus, limits its applicability to small- and medium-sized molecules. To avoid this scaling, we derive equations of motion for a series of truncated MCTDH methods using a many-mode second-quantization formulation where the configuration space is restricted based on mode-combination levels as also done in the vibrational configuration interaction and vibrational coupled cluster methods for solving the time-independent Schrödinger equation. The full MCTDH wave function is invariant with respect to the choice of constraint (or gauge) operators, but restricting the configuration space removes this invariance. We, thus, analyze the remaining redundancies and derive equations for variationally optimizing the non-redundant matrix elements of the constraint operators. As an alternative, we also present a constraint that keeps the density matrices block diagonal during the propagation and the two choices are compared. Example calculations are performed on formyl fluoride and a series of high-dimensional Henon–Heiles potentials. The results show that the MCTDH[n] methods can be applied to large systems and that an optimal choice of constraint operators is key to obtaining the correct physical behavior of the wave function. [ABSTRACT FROM AUTHOR]

We extend the coupled-cluster method to correlated quantum dynamics of both closed and open systems at finite temperatures using the thermofield formalism. The approach expresses the time-dependent density matrix in an exponential ansatz and describes time-evolution along the Keldysh path contour. A distinct advantage of the approach is exact trace-preservation as a function of time, ensuring conservation of probability and particle number. Furthermore, the method avoids the computation of correlated bra-states, simplifying the computational implementation. We develop the method in a thermal quasiparticle representation, which allows seamless connection to the projection method and diagrammatic techniques of the traditional coupled-cluster formalism. For comparison, we also apply the thermofield framework to the density-matrix renormalization-group method to obtain reference results for closed and open systems at finite temperature. We test the singles and doubles approximation to the density-matrix coupled-cluster method on the correlated electronic dynamics of the single-impurity Anderson model, demonstrating that the new method successfully captures the correlated dynamics of both closed systems at finite temperature and driven-dissipative open systems. This encouraging performance motivates future applications to nonequilibrium quantum many-body dynamics in realistic systems. [ABSTRACT FROM AUTHOR]

Density matrix embedding theory (DMET) is a quantum embedding theory for strongly correlated systems. From a computational perspective, one bottleneck in DMET is the optimization of the correlation potential to achieve self-consistency, especially for heterogeneous systems of large size. We propose a new method, called projected DMET (p-DMET), which achieves self-consistency without needing to optimize the correlation potential. We demonstrate the performance of p-DMET on the two-dimensional Hubbard model. [ABSTRACT FROM AUTHOR]

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The iterative decomposition of the blip-summed path integral [N. Makri, J. Chem. Phys. 141, 134117 (2014)] is described. The starting point is the expression of the reduced density matrix for a quantum system interacting with a harmonic dissipative bath in the form of a forward-backward path sum, where the effects of the bath enter through the Feynman-Vernon influence functional. The path sum is evaluated iteratively in time by propagating an array that stores blip configurations within the memory interval. Convergence with respect to the number of blips and the memory length yields numerically exact results which are free of statistical error. In situations of strongly dissipative, sluggish baths, the algorithm leads to a dramatic reduction of computational effort in comparison with iterative path integral methods that do not implement the blip decomposition. This gain in efficiency arises from (i) the rapid convergence of the blip series and (ii) circumventing the explicit enumeration of between-blip path segments, whose number grows exponentially with the memory length. Application to an asymmetric dissipative two-level system illustrates the rapid convergence of the algorithm even when the bath memory is extremely long. [ABSTRACT FROM AUTHOR]

We present a formalism that explicitly unifies the commonly used Nakajima-Zwanzig approach for reduced density matrix dynamics with the more versatile Mori theory in the context of nonequilibrium dynamics. Employing a Dyson-type expansion to circumvent the difficulty of projected dynamics, we obtain a self-consistent equation for the memory kernel which requires only knowledge of normally evolved auxiliary kernels. To illustrate the properties of the current approach, we focus on the spin-boson model and limit our attention to the use of a simple and inexpensive quasi-classical dynamics, given by the Ehrenfest method, for the calculation of the auxiliary kernels. For the first time, we provide a detailed analysis of the dependence of the properties of the memory kernels obtained via different projection operators, namely, the thermal (Redfield-type) and population based (NIBA-type) projection operators. We further elucidate the conditions that lead to short-lived memory kernels and the regions of parameter space to which this program is best suited. Via a thorough analysis of the different closures available for the auxiliary kernels and the convergence properties of the self-consistently extracted memory kernel, we identify the mechanisms whereby the current approach leads to a significant improvement over the direct usage of standard semi- and quasi-classical dynamics. [ABSTRACT FROM AUTHOR]

We propose a way of obtaining effective low energy Hubbard-like model Hamiltonians from ab initio quantum Monte Carlo calculations for molecular and extended systems. The Hamiltonian parameters are fit to best match the ab initio two-body density matrices and energies of the ground and excited states, and thus we refer to the method as ab initio density matrix based downfolding. For benzene (a finite system), we find good agreement with experimentally available energy gaps without using any experimental inputs. For graphene, a two dimensional solid (extended system) with periodic boundary conditions, we find the effective on-site HubbardU./t to be 1.3 ¡¾ 0.2, comparable to a recent estimate based on the constrained random phase approximation. For molecules, such parameterizations enable calculation of excited states that are usually not accessible within ground state approaches. For solids, the effective Hamiltonian enables large-scale calculations using techniques designed for lattice models. [ABSTRACT FROM AUTHOR]