Nonadiabatic simulations of exciton dissociation in poly-p-phenylenevinylene oligomers.

We present simulations of exciton dissociation and charge separation processes in the prototypical conjugated polymer, poly-p-phenylenevinylene. Our mixed quantum/classical simulations focus on the nonadiabatic excited state dynamics of single and pi-stacked oligomers of varying length. By applying a constant external electric field, our simulations reveal the details and time scale for exciton dissociation and fluorescence quenching and suggest how those processes relate to charge carrier (polaron) formation in polymer systems. We find that, in such a polarizing environment, sufficiently long chromophores (either single or interacting chains) can form polaron pairs via a delayed exciton dissociation mechanism or nearly instantaneously following photoexcitation. However, we find that these processes are mechanically essentially the same, being highly nonadiabatic in character and requiring transitions through "gateway" states to reach the completely charge separated electronic states. Finally, we observe thermally driven polaron hopping dynamics between chains, similar to the energy transfer dynamics we had described previously (J. Phys. Chem. A 2009, 113 (15), 3427). Our results are consistent with a range of apparently conflicting experiments, resolving some controversies regarding the molecular mechanism for charge carrier photogeneration in conjugated polymers.

Nonadiabatic mixed quantum-classical dynamic simulation of pi-stacked oligophenylenevinylenes.

We present results from the first nonadiabatic (NA), nonequilibrium mixed quantum-classical molecular dynamics simulations of pi-stacked oligophenylvinylene (OPV) chains with a quantum electronic Hamiltonian (Pariser-Parr-Pople with excited states given by configuration interaction) that goes beyond the tight-binding approximation. The chains pack approximately 3.6 A apart in the ground state at 300 K, and we discuss how thermal motions, chiefly a relative sliding motion along the oligomer backbone, affect the electronic structure. We assign the electronic absorption spectrum primarily to the S(0) --> S(2) transition as transitions from the ground state to S(1) and S(3) are particularly weak. After photoexcitation, the system rapidly decays via NA transitions to S(1) in under 150 fs. On S(1), the system relaxes as a bound exciton, localized on one chain that may hop between chains with a characteristic time between 300 and 800 fs. We find that the system does not make a rapid transition to the ground state because both the NA and radiative couplings between S(1) and S(0) are weak.

Moving solvated electrons with light: nonadiabatic mixed quantum/classical molecular dynamics simulations of the relocalization of photoexcited solvated electrons in tetrahydrofuran (THF).

Motivated by recent ultrafast spectroscopic experiments [Martini et al., Science 293, 462 (2001)], which suggest that photoexcited solvated electrons in tetrahydrofuran (THF) can relocalize (that is, return to equilibrium in solvent cavities far from where they started), we performed a series of nonequilibrium, nonadiabatic, mixed quantum/classical molecular dynamics simulations that mimic one-photon excitation of the THF-solvated electron. We find that as photoexcited THF-solvated electrons relax to their ground states either by continuous mixing from the excited state or via nonadiabatic transitions, approximately 30% of them relocalize into cavities that can be over 1 nm away from where they originated, in close agreement with the experiments. A detailed investigation shows that the ability of excited THF-solvated electrons to undergo photoinduced relocalization stems from the existence of preexisting cavity traps that are an intrinsic part of the structure of liquid THF. This explains why solvated electrons can undergo photoinduced relocalization in solvents like THF but not in solvents like water, which lack the preexisting traps necessary to stabilize the excited electron in other places in the fluid. We also find that even when they do not ultimately relocalize, photoexcited solvated electrons in THF temporarily visit other sites in the fluid, explaining why the photoexcitation of THF-solvated electrons is so efficient at promoting recombination with nearby scavengers. Overall, our study shows that the defining characteristic of a liquid that permits the photoassisted relocalization of solvated electrons is the existence of nascent cavities that are attractive to an excess electron; we propose that other such liquids can be found from classical computer simulations or neutron diffraction experiments.

Exploring the role of decoherence in condensed-phase nonadiabatic dynamics: a comparison of different mixed quantum/classical simulation algorithms for the excited hydrated electron.

Mixed quantum/classical (MQC) molecular dynamics simulation has become the method of choice for simulating the dynamics of quantum mechanical objects that interact with condensed-phase systems. There are many MQC algorithms available, however, and in cases where nonadiabatic coupling is important, different algorithms may lead to different results. Thus, it has been difficult to reach definitive conclusions about relaxation dynamics using nonadiabatic MQC methods because one is never certain whether any given algorithm includes enough of the necessary physics. In this paper, we explore the physics underlying different nonadiabatic MQC algorithms by comparing and contrasting the excited-state relaxation dynamics of the prototypical condensed-phase MQC system, the hydrated electron, calculated using different algorithms, including: fewest-switches surface hopping, stationary-phase surface hopping, and mean-field dynamics with surface hopping. We also describe in detail how a new nonadiabatic algorithm, mean-field dynamics with stochastic decoherence (MF-SD), is to be implemented for condensed-phase problems, and we apply MF-SD to the excited-state relaxation of the hydrated electron. Our discussion emphasizes the different ways quantum decoherence is treated in each algorithm and the resulting implications for hydrated-electron relaxation dynamics. We find that for three MQC methods that use Tully's fewest-switches criterion to determine surface hopping probabilities, the excited-state lifetime of the electron is the same. Moreover, the nonequilibrium solvent response function of the excited hydrated electron is the same with all of the nonadiabatic MQC algorithms discussed here, so that all of the algorithms would produce similar agreement with experiment. Despite the identical solvent response predicted by each MQC algorithm, we find that MF-SD allows much more mixing of multiple basis states into the quantum wave function than do other methods. This leads to an excited-state lifetime that is longer with MF-SD than with any method that incorporates nonadiabatic effects with the fewest-switches surface hopping criterion.

Projections of quantum observables onto classical degrees of freedom in mixed quantum-classical simulations: understanding linear response failure for the photoexcited hydrated electron.

We present a general analytic method for understanding how specific motions of a classical bath influence the dynamics of quantum-mechanical observables in mixed quantum-classical molecular dynamics simulations. We apply our method and develop expressions for the special case of quantum solvation, allowing us to examine how specific classical solvent motions couple to the equilibrium energy fluctuations and nonequilibrium energy relaxation of a quantum-mechanical solute. As a first application of our formalism, we investigate the motions of classical water underlying the equilibrium and nonequilibrium excited-state solvent response functions of the hydrated electron; the results allow us to explain why the linear response approximation fails for this system.

The role of solvent structure in the absorption spectrum of solvated electrons: mixed quantum/classical simulations in tetrahydrofuran.

In polar fluids such as water and methanol, the peak of the solvated electron's absorption spectrum in the red has been assigned as a sum of transitions between an s-like ground state and three nearly degenerate p-like excited states bound in a quasispherical cavity. In contrast, in weakly polar solvents such as tetrahydrofuran (THF), the solvated electron has an absorption spectrum that peaks in the mid-infrared, but no definitive assignment has been offered about the origins of the spectrum or the underlying structure. In this paper, we present the results of adiabatic mixed quantum/classical molecular dynamic simulations of the solvated electron in THF, and provide a detailed explanation of the THF-solvated electron's absorption spectrum and electronic structure. Using a classical solvent model and a fully quantum mechanical excess electron, our simulations show that although the ground and first excited states are bound in a quasispherical cavity, a multitude of other, nearby solvent cavities support numerous, nearly degenerate, bound excited states that have little Franck-Condon overlap with the ground state. We show that these solvent cavities, which are partially polarized so that they act as electron trapping sites, are an inherent property of the way THF molecules pack in the liquid. The absorption spectrum is thus assigned to a sum of bound-to-bound transitions between a localized ground state and multiple disjoint excited states scattered throughout the fluid. Furthermore, we find that the usual spherical harmonic labels (e.g., s-like, p-like) are not good descriptors of the excited-state wave functions of the solvated electron in THF. Our observation of multiple disjoint excited states is consistent with femtosecond pump-probe experiments in the literature that suggest that photoexcitation of solvated electrons in THF causes them to relocalize into solvent cavities far from where they originated.

Mean-field dynamics with stochastic decoherence (MF-SD): a new algorithm for nonadiabatic mixed quantum/classical molecular-dynamics simulations with nuclear-induced decoherence.

The key factors that distinguish algorithms for nonadiabatic mixed quantum/classical (MQC) simulations from each other are how they incorporate quantum decoherence-the fact that classical nuclei must eventually cause a quantum superposition state to collapse into a pure state-and how they model the effects of decoherence on the quantum and classical subsystems. Most algorithms use distinct mechanisms for modeling nonadiabatic transitions between pure quantum basis states ("surface hops") and for calculating the loss of quantum-mechanical phase information (e.g., the decay of the off-diagonal elements of the density matrix). In our view, however, both processes should be unified in a single description of decoherence. In this paper, we start from the density matrix of the total system and use the frozen Gaussian approximation for the nuclear wave function to derive a nuclear-induced decoherence rate for the electronic degrees of freedom. We then use this decoherence rate as the basis for a new nonadiabatic MQC molecular-dynamics (MD) algorithm, which we call mean-field dynamics with stochastic decoherence (MF-SD). MF-SD begins by evolving the quantum subsystem according to the time-dependent Schrodinger equation, leading to mean-field dynamics. MF-SD then uses the nuclear-induced decoherence rate to determine stochastically at each time step whether the system remains in a coherent mixed state or decoheres. Once it is determined that the system should decohere, the quantum subsystem undergoes an instantaneous total wave-function collapse onto one of the adiabatic basis states and the classical velocities are adjusted to conserve energy. Thus, MF-SD combines surface hops and decoherence into a single idea: decoherence in MF-SD does not require the artificial introduction of reference states, auxiliary trajectories, or trajectory swarms, which also makes MF-SD much more computationally efficient than other nonadiabatic MQC MD algorithms. The unified definition of decoherence in MF-SD requires only a single ad hoc parameter, which is not adjustable but instead is determined by the spatial extent of the nonadiabatic coupling. We use MF-SD to solve a series of one-dimensional scattering problems and find that MF-SD is as quantitatively accurate as several existing nonadiabatic MQC MD algorithms and significantly more accurate for some problems.