Unified Formulation of Phase Space Mapping Approaches for Nonadiabatic Quantum Dynamics.
TL;DR: In this paper, a unified framework for constructing the mapping Hamiltonian on phase space for coupled F-state systems where the renowned Meyer-Miller Hamiltonian model is a special case is presented.
Abstract: ConspectusNonadiabatic dynamical processes are one of the most important quantum mechanical phenomena in chemical, materials, biological, and environmental molecular systems, where the coupling between different electronic states is either inherent in the molecular structure or induced by the (intense) external field. The curse of dimensionality indicates the intractable exponential scaling of calculation effort with system size and restricts the implementation of "numerically exact" approaches for realistic large systems. The phase space formulation of quantum mechanics offers an important theoretical framework for constructing practical approximate trajectory-based methods for quantum dynamics. This Account reviews our recent progress in phase space mapping theory: a unified framework for constructing the mapping Hamiltonian on phase space for coupled F-state systems where the renowned Meyer-Miller Hamiltonian model is a special case, a general phase space formulation of quantum mechanics for nonadiabatic systems where the electronic degrees of freedom are mapped onto constraint space and the nuclear degrees of freedom are mapped onto infinite space, and an isomorphism between the mapping phase space approach for nonadiabatic systems and that for nonequilibrium electron transport processes. While the zero-point-energy parameter is conventionally assumed to be positive, we show that the constraint implied in the conventional Meyer-Miller mapping Hamiltonian requires that such a parameter can be negative as well and lies in (-1/F, +∞) for each electronic degree of freedom. More importantly, the zero-point-energy parameter should be interpreted as a special case of a commutator matrix in the comprehensive phase space mapping Hamiltonian for nonadiabatic systems. From the rigorous formulation of mapping phase space, we propose approximate but practical trajectory-based nonadiabatic dynamics methods. The applications to both gas phase and condensed phase problems include the spin-boson model for condensed phase dissipative two-state systems, the three-state photodissociation models, the seven-site model of the Fenna-Matthews-Olson monomer in photosynthesis of green sulfur bacteria, the strongly coupled molecular/atomic matter-optical cavity systems designed for controlling and manipulating chemical dynamical processes, and the Landauer model for a quantum dot state coupled with two electrodes. In these applications the overall performance of our phase space mapping dynamics approach is superior to two prevailing trajectory-based methods, Ehrenfest dynamics and fewest switches surface hopping.
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TL;DR: In this paper , a review of the fundamental algorithms of TD-DMRG in the modern framework of matrix product states (MPS) and matrix product operators (MPO), including the basic algebra with respect to MPS and MPO, the novel time evolution schemes to propagate MPS, and the automated MPO construction algorithm to encode generic Hamiltonian.
Abstract: The simulations of spectroscopy and quantum dynamics are of vital importance to the understanding of the electronic processes in complex systems, including the radiative/radiationless electronic relaxation relevant for optical emission, charge/energy transfer in molecular aggregates related to carrier mobility in organic materials, as well as photovoltaic and thermoelectric conversion, light‐harvesting and spin transport, and so forth. In recent years, time‐dependent density matrix renormalization group (TD‐DMRG) has emerged as a general, numerically accurate and efficient method for high‐dimensional full‐quantum dynamics. This review will cover the fundamental algorithms of TD‐DMRG in the modern framework of matrix product states (MPS) and matrix product operators (MPO), including the basic algebra with respect to MPS and MPO, the novel time evolution schemes to propagate MPS, and the automated MPO construction algorithm to encode generic Hamiltonian. Most importantly, the proposed method can handle the mixed state density matrix at finite temperature, enabling quantum statistical description for molecular aggregates. We demonstrate the performance of TD‐DMRG by benchmarking with the current state‐of‐the‐art methods for simulating quantum dynamics of the spin‐boson model and the Frenkel–Holstein(–Peierls) model. As applications of TD‐DMRG to real‐world problems, we present theoretical investigations of carrier mobility and spectral function of rubrene crystal, and the radiationless decay rate of azulene with an anharmonic potential energy surface.
16 citations
TL;DR: In this article , an AI-QD approach using AI to directly predict QD as a function of time and other parameters such as temperature, reorganization energy, etc., completely circumventing the need of recursive step-wise dynamics propagation in contrast to the traditional QD and alternative, recursive AI-based QD approaches.
Abstract: Exploring excitation energy transfer (EET) in light-harvesting complexes (LHCs) is essential for understanding the natural processes and design of highly-efficient photovoltaic devices. LHCs are open systems, where quantum effects may play a crucial role for almost perfect utilization of solar energy. Simulation of energy transfer with inclusion of quantum effects can be done within the framework of dissipative quantum dynamics (QD), which are computationally expensive. Thus, artificial intelligence (AI) offers itself as a tool for reducing the computational cost. Here we suggest AI-QD approach using AI to directly predict QD as a function of time and other parameters such as temperature, reorganization energy, etc., completely circumventing the need of recursive step-wise dynamics propagation in contrast to the traditional QD and alternative, recursive AI-based QD approaches. Our trajectory-learning AI-QD approach is able to predict the correct asymptotic behavior of QD at infinite time. We demonstrate AI-QD on seven-sites Fenna-Matthews-Olson (FMO) complex.
11 citations
TL;DR: In this paper , the authors report progress on the phase space formulation of quantum mechanics with coordinatemomentum variables, focusing more on new theory of (weighted) constraint coordinate momentum phase space for discrete variable quantum systems.
Abstract: We report recent progress on the phase space formulation of quantum mechanics with coordinate‐momentum variables, focusing more on new theory of (weighted) constraint coordinate‐momentum phase space for discrete‐variable quantum systems. This leads to a general coordinate‐momentum phase space formulation of composite quantum systems, where conventional representations on infinite phase space are employed for continuous variables. It is convenient to utilize (weighted) constraint coordinate‐momentum phase space for representing the quantum state and describing nonclassical features. Various numerical tests demonstrate that new trajectory‐based quantum dynamics approaches derived from the (weighted) constraint phase space representation are useful and practical for describing dynamical processes of composite quantum systems in the gas phase as well as in the condensed phase.
7 citations
TL;DR: In this article , the generalized spin mapping representation for non-adiabatic dynamics is presented, where the Stratonovich-Weyl transform is used to map an operator in the Hilbert space to a continuous function on the SU(N) Lie group.
Abstract: We present the rigorous theoretical framework of the generalized spin mapping representation for non-adiabatic dynamics. Our work is based upon a new mapping formalism recently introduced by Runeson and Richardson [J. Chem. Phys. 152, 084110 (2020)], which uses the generators of the su(N) Lie algebra to represent N discrete electronic states, thus preserving the size of the original Hilbert space. Following this interesting idea, the Stratonovich-Weyl transform is used to map an operator in the Hilbert space to a continuous function on the SU(N) Lie group, i.e., a smooth manifold which is a phase space of continuous variables. We further use the Wigner representation to describe the nuclear degrees of freedom and derive an exact expression of the time-correlation function as well as the exact quantum Liouvillian for the non-adiabatic system. Making the linearization approximation, this exact Liouvillian is reduced to the Liouvillian of several recently proposed methods, and the performance of this linearized method is tested using non-adiabatic models. We envision that the theoretical work presented here provides a rigorous and unified framework to formally derive non-adiabatic quantum dynamics approaches with continuous variables and connects the previous methods in a clear and concise manner.
6 citations
TL;DR: A one-shot trajectory learning approach that allows us to directly make an ultrafast prediction of the entire trajectory of the reduced density matrix for a new set of such simulation parameters as temperature and reorganization energy.
Abstract: Nonadiabatic quantum dynamics is important for understanding light-harvesting processes, but its propagation with traditional methods can be rather expensive. Here we present a one-shot trajectory learning approach that allows us to directly make an ultrafast prediction of the entire trajectory of the reduced density matrix for a new set of such simulation parameters as temperature and reorganization energy. The whole 10-ps-long propagation takes 70 ms as we demonstrate on the comparatively large quantum system, the Fenna-Matthews-Olsen (FMO) complex. Our approach also significantly reduces time and memory requirements for training.
6 citations
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TL;DR: In this article, the Boltzmann formula for the probability of a configuration is given in classical theory by means of a probability function, and the result discussed is developed for the correction term.
Abstract: The probability of a configuration is given in classical theory by the Boltzmann formula $\mathrm{exp}[\ensuremath{-}\frac{V}{\mathrm{hT}}]$ where $V$ is the potential energy of this configuration. For high temperatures this of course also holds in quantum theory. For lower temperatures, however, a correction term has to be introduced, which can be developed into a power series of $h$. The formula is developed for this correction by means of a probability function and the result discussed.
6,791 citations
TL;DR: In der Anwendung der Quantentheorie auf die Molekeln kann man folgende Entwicklungsstufen unterscheiden: Das erste Stadium1) ersetzt die zweiatomige Molekel durch das Hantelmodell, das als einfacher „Rotator“ behandelt wird as discussed by the authors.
Abstract: In der Anwendung der Quantentheorie auf die Molekeln kann man folgende Entwicklungsstufen unterscheiden: Das erste Stadium1) ersetzt die zweiatomige Molekel durch das Hantelmodell, das als einfacher „Rotator“ behandelt wird. Mehratomige Molekeln werden in entsprechender Weise als starre „Kreisel“ angesehen.2) Dieser Standpunkt erlaubt es, die einfachsten Gesetze der Bandenspektren und der spezifischen Warme mehratomiger Gase zu erklaren. Das nachste Stadium1) last die Annahme starrer Verbindungen zwischen den Atomen fallen und berucksichtigt die Kernschwingungen, zunachst als harmonische Schwingungen; dabie ergenben sich nach Sponer3) und Kratzer4) Zusammenhange zwischen den einzelnen Banden eines Bandensystems.
4,131 citations
TL;DR: In this article, a functional-integral approach to the dynamics of a two-state system coupled to a dissipative environment is presented, and an exact and general prescription for the reduction, under appropriate circumstances, of the problem of a system tunneling between two wells in the presence of dissipative environments to the spin-boson problem is given.
Abstract: This paper presents the results of a functional-integral approach to the dynamics of a two-state system coupled to a dissipative environment. It is primarily an extended account of results obtained over the last four years by the authors; while they try to provide some background for orientation, it is emphatically not intended as a comprehensive review of the literature on the subject. Its contents include (1) an exact and general prescription for the reduction, under appropriate circumstances, of the problem of a system tunneling between two wells in the presence of a dissipative environment to the "spin-boson" problem; (2) the derivation of an exact formula for the dynamics of the latter problem; (3) the demonstration that there exists a simple approximation to this exact formula which is controlled, in the sense that we can put explicit bounds on the errors incurred in it, and that for almost all regions of the parameter space these errors are either very small in the limit of interest to us (the "slow-tunneling" limit) or can themselves be evaluated with satisfactory accuracy; (4) use of these results to obtain quantitative expressions for the dynamics of the system as a function of the spectral density $J(\ensuremath{\omega})$ of its coupling to the environment. If $J(\ensuremath{\omega})$ behaves as ${\ensuremath{\omega}}^{s}$ for frequencies of the order of the tunneling frequency or smaller, the authors find for the "unbiased" case the following results: For $sl1$ the system is localized at zero temperature, and at finite $T$ relaxes incoherently at a rate proportional to $\mathrm{exp}\ensuremath{-}{(\frac{{T}_{0}}{T})}^{1\ensuremath{-}s}$. For $sg2$ it undergoes underdamped coherent oscillations for all relevant temperatures, while for $1lsl2$ there is a crossover from coherent oscillation to overdamped relaxation as $T$ increases. Exact expressions for the oscillation and/or relaxation rates are presented in all these cases. For the "ohmic" case, $s=1$, the qualitative nature of the behavior depends critically on the dimensionless coupling strength $\ensuremath{\alpha}$ as well as the temperature $T$: over most of the ($\ensuremath{\alpha}$,$T$) plane (including the whole region $\ensuremath{\alpha}g1$) the behavior is an incoherent relaxation at a rate proportional to ${T}^{2\ensuremath{\alpha}\ensuremath{-}1}$, but for low $T$ and $0l\ensuremath{\alpha}l\frac{1}{2}$ the authors predict a combination of damped coherent oscillation and incoherent background which appears to disagree with the results of all previous approximations. The case of finite bias is also discussed.
4,047 citations
TL;DR: In this article, a method for carrying out molecular dynamics simulations of processes that involve electronic transitions is proposed, where the time dependent electronic Schrodinger equation is solved self-consistently with the classical mechanical equations of motion of the atoms.
Abstract: A method is proposed for carrying out molecular dynamics simulations of processes that involve electronic transitions. The time dependent electronic Schrodinger equation is solved self‐consistently with the classical mechanical equations of motion of the atoms. At each integration time step a decision is made whether to switch electronic states, according to probabilistic ‘‘fewest switches’’ algorithm. If a switch occurs, the component of velocity in the direction of the nonadiabatic coupling vector is adjusted to conserve energy. The procedure allows electronic transitions to occur anywhere among any number of coupled states, governed by the quantum mechanical probabilities. The method is tested against accurate quantal calculations for three one‐dimensional, two‐state models, two of which have been specifically designed to challenge any such mixed classical–quantal dynamical theory. Although there are some discrepancies, initial indications are encouraging. The model should be applicable to a wide variety of gas‐phase and condensed‐phase phenomena occurring even down to thermal energies.
3,173 citations
TL;DR: In this article, it was shown that it is possible to build up a fairly satisfactory theory of the emission of radiation and of the reaction of the radiation field on the emitting system on the basis of a kinematics and dynamics which are not strictly relativistic.
Abstract: The new quantum theory, based on the assumption that the dynamical variables do not obey the commutative law of multiplication, has by now been developed sufficiently to form a fairly complete theory of dynamics. One can treat mathematically the problem of any dynamical system composed of a number of particles with instantaneous forces acting between them, provided it is describable by a Hamiltonian function, and one can interpret the mathematics physically by a quite definite general method. On the other hand, hardly anything has been done up to the present on quantum electrodynamics. The questions of the correct treatment of a system in which the forces are propagated with the velocity of light instead of instantaneously, of the production of an electromagnetic field by a moving electron, and of the reaction of this field on the electron have not yet been touched. In addition, there is a serious difficulty in making the theory satisfy all the requirements of the restricted principle of relativity, since a Hamiltonian function can no longer be used. This relativity question is, of course, connected with the previous ones, and it will be impossible to answer any one question completely without at the same time answering them all. However, it appears to be possible to build up a fairly satisfactory theory of the emission of radiation and of the reaction of the radiation field on the emitting system on the basis of a kinematics and dynamics which are not strictly relativistic.
1,774 citations