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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]

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]

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]

The switching of single cyclooctadiene molecules chemisorbed on a Si(100) surface between two stable conformations, can be achieved with a scanning tunneling microscope [Nacci et al., Phys. Rev. B 77, 121405(R) (2008)]. Recently, it was shown by quantum chemical and quantum dynamical simulations that major experimental facts can be explained by a single-mode model with switching enforced by inelastic electron tunneling (IET) excitations and perturbed by vibrational relaxation [Nacci et al., Nano Lett. 9, 2997 (2009)]. In the present paper, we extend the previous theoretical work in several respects: (1) The model is generalized to a two-mode description in which two C2H4 units of COD can move independently; (2) contributions of dipole and, in addition, (cation and anion) resonance-IET rates are considered; (3) the harmonic-linear vibrational relaxation model used previously is generalized to anharmonic vibrations. While the present models highlight generic aspects of IET-switching between two potential minima, they also rationalize specific experimental findings for COD/Si(100): (1) A single-electron excitation mechanism with a linear dependence of the switching rate on tunneling current I, (2) the capability to switch both at negative and positive sample biases, and (3) a crossover temperature around ∼60 K from an IET-driven, T-independent atom tunneling regime, to classical over-the-barrier isomerization with exponential T-dependence at higher temperatures for a bias voltage of +1.5 V and an average tunneling current of 0.73 nA. [ABSTRACT FROM AUTHOR]

This paper presents a new approach to propagating the density matrix based on a time stepping procedure arising from a Trotter factorization and combining the forward and backward incremental propagators. The sums over intermediate states of the discrete quantum subsystem are implemented by a Monte Carlo surface hopping-like procedure, while the integrals over the continuous variables are performed using a linearization in the difference between the forward and backward paths of these variables leading to classical-like equations of motion with forces determined by the quantum subsystem states. The approach is tested on several models and numerical convergence is explored. [ABSTRACT FROM AUTHOR]

The reformulation of the standard golden rule approach considered in this paper for treating reactive tunneling reduces the computation of the reaction rate to a derivation of band shapes for energy levels of reactant and product states. This treatment is based on the assumption that the medium environment is actively involved as a partner in the energy exchange with the reactive subsystem but its reorganization effect is negligible. Starting from the quantum relaxation equation for the density matrix, the required band shapes are represented in terms of the spectral density function, exhibiting the continuum spectrum inherent to the interaction between the reactants and the medium in the total reactive system. The simplest Lorentzian spectral bands, obtained under Redfield approximation, proved to be unsatisfactory because they produced a divergent rate expression at low temperature. The problem is resolved by invoking a refined spectral band shape, which behaves as Lorentzian one at the band center but decays exponentially at its tails. The corresponding closed non-Markovian rate expression is derived and investigated taking as an example the photochemical H-transfer reaction between fluorene and acridine proceeding in the fluorene molecular crystal. The kinetics in this reactive system was thoroughly studied experimentally in a wide temperature range [B. Prass et al., Ber. Bunsenges. Phys. Chem. 102, 498 (1998)]. [ABSTRACT FROM AUTHOR]

Errors in the control of quantum systems may be classified as unitary, decoherent, and incoherent. Unitary errors are systematic, and result in a density matrix that differs from the desired one by a unitary operation. Decoherent errors correspond to general completely positive superoperators, and can only be corrected using methods such as quantum error correction. Incoherent errors can also be described, on average, by completely positive superoperators, but can nevertheless be corrected by the application of a locally unitary operation that “refocuses” them. They are due to reproducible spatial or temporal variations in the system’s Hamiltonian, so that information on the variations is encoded in the system’s spatiotemporal state and can be used to correct them. In this paper liquid-state nuclear magnetic resonance is used to demonstrate that such refocusing effects can be built directly into the control fields, where the incoherence arises from spatial inhomogeneities in the quantizing static magnetic field as well as the radio-frequency control fields themselves. Using perturbation theory, it is further shown that the eigenvalue spectrum of the completely positive superoperator exhibits a characteristic spread that contains information on the Hamiltonians’ underlying distribution. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

For common condensed phase problems described by a low-dimensional system coupled to a harmonic bath, Feynman’s path integral formulation of time-dependent quantum mechanics leads to expressions for the reduced density matrix of the system where the effects of the harmonic environment enter through an influence functional that is nonlocal in time. In a recent Letter [Chem. Phys. Lett. 221, 482 (1994)], we demonstrated that the range of the nonlocal interactions is finite even at zero temperature, such that the nonlocal kernel extends over only a few time steps if the path integral is expressed in terms of accurate quasiadiabatic propagators. This feature arises from disruption of phase coherence in macroscopic environments and leads to Markovian dynamics for an augmented reduced density tensor, permitting iterative time evolution schemes. In the present paper we analyze the structure and properties of the relevant tensor propagator. Specifically, we show that the tensor multiplication scheme rigorously conserves the trace of the reduced density matrix, and that in cases of short-range nonlocality it leads to Redfield-type equations which are correct to all orders in perturbation theory and which take into account memory effects. We also argue that a simple eigenvector analysis reveals (without actual iteration) the nature of the dynamics and of the equilibrium state, and directly yields quantum reaction or relaxation rates. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In a recent Letter [Chem. Phys. Lett. 221, 482 (1994)], we demonstrated that the dynamics of reduced density matrices for systems in contact with dissipative harmonic environments can be obtained in an iterative fashion by multiplication of a propagator tensor. The feasibility of iterative procedures in reduced dimension spaces arises from intrinsic features of the dissipative influence functional in Feynman’s path integral formulation of quantum dynamics. Specifically, the continuum of frequencies characteristic of broad condensed phase spectra disrupts phase coherence to a large extent, such that the dynamics of an augmented reduced density tensor becomes Markovian. In a preceding article [J. Chem. Phys. 102, 4600 (1995)] we examined in detail the formal properties of the tensor propagator. In the present paper we show that the tensor propagator can be further decomposed into a product of small rank tensors, resulting in an extremely simple and efficient numerical scheme that scales almost linearly with the dimension of the augmented reduced density tensor. Numerical application to a model electron transfer reaction is presented. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In this paper, we investigate coherent quantum dynamics in a nonequilibrium environment. We focus on a two-state quantum system strongly coupled to a single classical environmental oscillator, and explore the effect of nonstationary statistical properties of the oscillator on the quantum evolution. A simple nonequilibrium model, consisting of an oscillator with a well-defined initial phase which undergoes subsequent diffusion, is introduced and studied. Approximate but accurate analytic expressions for the evolution of the off-diagonal density matrix element of the quantum system are derived in the second-order cumulant approximation. The effect of the initial phase choice on the subsequent quantum evolution is quantified. It is observed that the initial phase can have a significant effect on the preservation of coherence on short time scales, suggesting this variable as a control parameter for optimizing coherence in many-body quantum systems. [ABSTRACT FROM AUTHOR]