Non-adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials.

Optically active molecular materials, such as organic conjugated polymers and biological systems, are characterized by strong coupling between electronic and vibrational degrees of freedom. Typically, simulations must go beyond the Born-Oppenheimer approximation to account for non-adiabatic coupling between excited states. Indeed, non-adiabatic dynamics is commonly associated with exciton dynamics and photophysics involving charge and energy transfer, as well as exciton dissociation and charge recombination. Understanding the photoinduced dynamics in such materials is vital to providing an accurate description of exciton formation, evolution, and decay. This interdisciplinary field has matured significantly over the past decades. Formulation of new theoretical frameworks, development of more efficient and accurate computational algorithms, and evolution of high-performance computer hardware has extended these simulations to very large molecular systems with hundreds of atoms, including numerous studies of organic semiconductors and biomolecules. In this Review, we will describe recent theoretical advances including treatment of electronic decoherence in surface-hopping methods, the role of solvent effects, trivial unavoided crossings, analysis of data based on transition densities, and efficient computational implementations of these numerical methods. We also emphasize newly developed semiclassical approaches, based on the Gaussian approximation, which retain phase and width information to account for significant decoherence and interference effects while maintaining the high efficiency of surface-hopping approaches. The above developments have been employed to successfully describe photophysics in a variety of molecular materials.

Improved Ehrenfest Approach to Model Correlated Electron-Nuclear Dynamics.

Mixed quantum-classical mechanical descriptions are critical to modeling coupled electron-nuclear dynamics, i.e., nonadiabatic molecular dynamics, relevant to photochemical and photophysical processes. We introduce an efficient description of such dynamics in terms of an effective Hamiltonian that not only properly captures electron-nuclear correlation effects but also helps develop an efficient computational method. In particular, we introduce a coupled Gaussian wavepacket parametrization of the nuclear wave function, which generalizes the Ehrenfest approach to account for electron-nuclei correlations. We test this new approach, Ehrenfest-Plus, on a suite of model problems that probe electron-nuclear correlation in nonadiabatic transitions. The high accuracy of our approach, combined with mixed quantum-classical efficiency, opens a path for improved simulation of nonadiabatic molecular dynamics in realistic molecular systems.

Coupled wave-packets for non-adiabatic molecular dynamics: a generalization of Gaussian wave-packet dynamics to multiple potential energy surfaces.

Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semi-classical approximation, that is as efficient as the commonly used mean field Ehrenfest or ad hoc surface hopping methods and properly accounts for interference and decoherence effects. This novel method is an extension of Heller's thawed Gaussian wave-packet dynamics that includes coupling between potential energy surfaces. By studying several standard test problems we demonstrate that the accuracy of the method can be systematically improved while maintaining high efficiency. The method is suitable for investigating the role of quantum coherence in the non-adiabatic dynamics of many-atom molecules.

Non-adiabatic molecular dynamics by accelerated semiclassical Monte Carlo.

Non-adiabatic dynamics, where systems non-radiatively transition between electronic states, plays a crucial role in many photo-physical processes, such as fluorescence, phosphorescence, and photoisomerization. Methods for the simulation of non-adiabatic dynamics are typically either numerically impractical, highly complex, or based on approximations which can result in failure for even simple systems. Recently, the Semiclassical Monte Carlo (SCMC) approach was developed in an attempt to combine the accuracy of rigorous semiclassical methods with the efficiency and simplicity of widely used surface hopping methods. However, while SCMC was found to be more efficient than other semiclassical methods, it is not yet as efficient as is needed to be used for large molecular systems. Here, we have developed two new methods: the accelerated-SCMC and the accelerated-SCMC with re-Gaussianization, which reduce the cost of the SCMC algorithm up to two orders of magnitude for certain systems. In most cases shown here, the new procedures are nearly as efficient as the commonly used surface hopping schemes, with little to no loss of accuracy. This implies that these modified SCMC algorithms will be of practical numerical solutions for simulating non-adiabatic dynamics in realistic molecular systems.

Semiclassical Monte Carlo: a first principles approach to non-adiabatic molecular dynamics.

Modeling the dynamics of photophysical and (photo)chemical reactions in extended molecular systems is a new frontier for quantum chemistry. Many dynamical phenomena, such as intersystem crossing, non-radiative relaxation, and charge and energy transfer, require a non-adiabatic description which incorporate transitions between electronic states. Additionally, these dynamics are often highly sensitive to quantum coherences and interference effects. Several methods exist to simulate non-adiabatic dynamics; however, they are typically either too expensive to be applied to large molecular systems (10's-100's of atoms), or they are based on ad hoc schemes which may include severe approximations due to inconsistencies in classical and quantum mechanics. We present, in detail, an algorithm based on Monte Carlo sampling of the semiclassical time-dependent wavefunction that involves running simple surface hopping dynamics, followed by a post-processing step which adds little cost. The method requires only a few quantities from quantum chemistry calculations, can systematically be improved, and provides excellent agreement with exact quantum mechanical results. Here we show excellent agreement with exact solutions for scattering results of standard test problems. Additionally, we find that convergence of the wavefunction is controlled by complex valued phase factors, the size of the non-adiabatic coupling region, and the choice of sampling function. These results help in determining the range of applicability of the method, and provide a starting point for further improvement.

Semiclassical Monte-Carlo approach for modelling non-adiabatic dynamics in extended molecules.

Modelling of non-adiabatic dynamics in extended molecular systems and solids is a next frontier of atomistic electronic structure theory. The underlying numerical algorithms should operate only with a few quantities (that can be efficiently obtained from quantum chemistry), provide a controlled approximation (which can be systematically improved) and capture important phenomena such as branching (multiple products), detailed balance and evolution of electronic coherences. Here we propose a new algorithm based on Monte-Carlo sampling of classical trajectories, which satisfies the above requirements and provides a general framework for existing surface hopping methods for non-adiabatic dynamics simulations. In particular, our algorithm can be viewed as a post-processing technique for analysing numerical results obtained from the conventional surface hopping approaches. Presented numerical tests for several model problems demonstrate efficiency and accuracy of the new method.

Metastable states and macroscopic quantum tunneling in a cold-atom Josephson ring.

We study macroscopic properties of a system of weakly interacting neutral bosons confined in a ring-shaped potential with a Josephson junction. We derive an effective low energy action for this system and evaluate its properties. In particular, we find that the system possesses a set of metastable current-carrying states and evaluate the rates of transitions between these states due to macroscopic quantum tunneling and thermal activation mechanism. Finally, we discuss signatures of different metastable states in the time-of-flight images and argue that the effect is observable within currently available experimental technique.

Kinetics of the phase separation transition in cold-atom boson-fermion mixtures.

We study the kinetics of the first order phase separation transition in boson-fermion cold-atom mixtures. At sufficiently low temperatures such a transition is driven by quantum fluctuations responsible for the formation of critical nuclei of a stable phase. Based on a microscopic description of interacting boson-fermion mixtures we derive an effective action for the critical droplet and obtain an asymptotic expression for the nucleation rate in the vicinity of the phase transition and near the spinodal instability of the mixed phase. We also discuss effects of dissipation which play a dominant role close to the transition point, and identify the regimes where quantum nucleation can be experimentally observed in cold-atom systems.

Ion dynamics and energy relaxation rate in nonequilibrium electron-ion systems.

We rigorously derive an analytical expression for the energy equilibration rate in nonequilibrium electron-ion systems that is valid for a large class of systems including solid and liquid metals, warm dense matter, and hot, weakly coupled plasmas. To this end we first derive a generalized Langevin equation that describes the motion of the classical ions in the quantum mechanical environment of the electrons. A general expression for the energy relaxation rate is then obtained assuming that each subsystem is in thermal equilibrium with itself. Direct approximations naturally reproduce the popular results of Landau and Spitzer for hot plasmas and the "Fermi golden rule" result for dense matter. We propose a method to evaluate numerically the energy relaxation rate with finite-temperature density functional theory calculations in difficult regimes such as the warm dense matter regime where neither quantum nor strong coupling effects can be ignored.