Vibronic coupling models for donor-acceptor aggregates using an effective-mode scheme: Application to mixed Frenkel and charge-transfer excitons in oligothiophene aggregates.

A reduced-dimensional effective-mode representation is developed in order to efficiently describe excited-state dynamics of multichromophoric donor-acceptor aggregates within a linear vibronic coupling model. Specifically, we consider systems where vibrational modes pertaining to a given molecular fragment couple both to local excitations of Frenkel type and delocalized states of charge transfer exciton type. A hierarchical chain representation is constructed which is suitable to describe correlated fluctuations, leading to a set of correlated spectral densities. An application is shown for a first-principles parameterized model of an oligothiophene H-type aggregate whose properties are modified due to the presence of charge transfer excitons. Within a pentamer model comprising 13 electronic states and 195 normal modes, good convergence of the effective-mode representation of the spectral densities is achieved at the eighth order of the hierarchy with 104 modes, and a qualitatively correct picture is obtained at the sixth order with 78 modes.

Quantum dynamics of hydrogen atoms on graphene. I. System-bath modeling.

An accurate system-bath model to investigate the quantum dynamics of hydrogen atoms chemisorbed on graphene is presented. The system comprises a hydrogen atom and the carbon atom from graphene that forms the covalent bond, and it is described by a previously developed 4D potential energy surface based on density functional theory ab initio data. The bath describes the rest of the carbon lattice and is obtained from an empirical force field through inversion of a classical equilibrium correlation function describing the hydrogen motion. By construction, model building easily accommodates improvements coming from the use of higher level electronic structure theory for the system. Further, it is well suited to a determination of the system-environment coupling by means of ab initio molecular dynamics. This paper details the system-bath modeling and shows its application to the quantum dynamics of vibrational relaxation of a chemisorbed hydrogen atom, which is here investigated at T = 0 K with the help of the multi-configuration time-dependent Hartree method. Paper II deals with the sticking dynamics.

Quantum dynamics of hydrogen atoms on graphene. II. Sticking.

Following our recent system-bath modeling of the interaction between a hydrogen atom and a graphene surface [Bonfanti et al., J. Chem. Phys. 143, 124703 (2015)], we present the results of converged quantum scattering calculations on the activated sticking dynamics. The focus of this study is the collinear scattering on a surface at zero temperature, which is treated with high-dimensional wavepacket propagations with the multi-configuration time-dependent Hartree method. At low collision energies, barrier-crossing dominates the sticking and any projectile that overcomes the barrier gets trapped in the chemisorption well. However, at high collision energies, energy transfer to the surface is a limiting factor, and fast H atoms hardly dissipate their excess energy and stick on the surface. As a consequence, the sticking coefficient is maximum (∼0.65) at an energy which is about one and half larger than the barrier height. Comparison of the results with classical and quasi-classical calculations shows that quantum fluctuations of the lattice play a primary role in the dynamics. A simple impulsive model describing the collision of a classical projectile with a quantum surface is developed which reproduces the quantum results remarkably well for all but the lowest energies, thereby capturing the essential physics of the activated sticking dynamics investigated.

Non-Markovian reduced dynamics based upon a hierarchical effective-mode representation.

A reduced dynamics representation is introduced which is tailored to a hierarchical, Mori-chain type representation of a bath of harmonic oscillators which are linearly coupled to a subsystem. We consider a spin-boson system where a single effective mode is constructed so as to absorb all system-environment interactions, while the residual bath modes are coupled bilinearly to the primary mode and among each other. Using a cumulant expansion of the memory kernel, correlation functions for the primary mode are obtained, which can be suitably approximated by truncated chains representing the primary-residual mode interactions. A series of reduced-dimensional bath correlation functions is thus obtained, which can be expressed as Fourier-Laplace transforms of spectral densities that are given in truncated continued-fraction form. For a master equation which is second order in the system-bath coupling, the memory kernel is re-expressed in terms of local-in-time equations involving auxiliary densities and auxiliary operators.

Maximum-entropy closure of hydrodynamic moment hierarchies including correlations.

Generalized hydrodynamic moment hierarchies are derived which explicitly include nonequilibrium two-particle and higher-order correlations. The approach is adapted to strongly correlated media and nonequilibrium processes on short time scales which necessitate an explicit treatment of time-evolving correlations. Closure conditions for the extended moment hierarchies are formulated by a maximum-entropy approach, generalizing related closure procedures for kinetic equations. A self-consistent set of nonperturbative dynamical equations are thus obtained for a chosen set of single-particle and two-particle (and possibly higher-order) moments. Analytical results are derived for generalized Gaussian closures including the dynamic pair distribution function and a two-particle correction to the current density. The maximum-entropy closure conditions are found to involve the Kirkwood superposition approximation.

Extended hydrodynamic approach to quantum-classical nonequilibrium evolution. II. Application to nonpolar solvation.

The mixed quantum-classical formulation derived in our companion paper [D. Bousquet, K. H. Hughes, D. Micha, and I. Burghardt, J. Chem. Phys. 134, 064116 (2011)], which is based upon a hydrodynamic representation of the classical sector, is applied to nonequilibrium nonpolar solvation dynamics as exemplified by the solvation of the electronically excited NO molecule in a rare gas environment. Derived from a partition of the Hamiltonian into a primary (quantum) part and a secondary (classical) part the hydrodynamic equations are formulated for multi-quantum states and result in explicit equations of motion for populations and coherences. The hierarchy of hydrodynamic equations is truncated by the following approximate closure schemes: Gauss-Hermite closure, dynamical density functional theory approximation, and a generalized Maxwellian closure. A comparison of the dynamics using these three closure methods showed that the suitability of a particular closure scheme was dependent on the initial conditions and the nonequilibrium character of the dynamics.

Extended hydrodynamic approach to quantum-classical nonequilibrium evolution. I. Theory.

A mixed quantum-classical formulation is developed for a quantum subsystem in strong interaction with an N-particle environment, to be treated as classical in the framework of a hydrodynamic representation. Starting from the quantum Liouville equation for the N-particle distribution and the corresponding reduced single-particle distribution, exact quantum hydrodynamic equations are obtained for the momentum moments of the single-particle distribution coupled to a discretized quantum subsystem. The quantum-classical limit is subsequently taken and the resulting hierarchy of equations is further approximated by various closure schemes. These include, in particular, (i) a Grad-Hermite-type closure, (ii) a Gaussian closure at the level of a quantum-classical local Maxwellian distribution, and (iii) a dynamical density functional theory approximation by which the hydrodynamic pressure term is replaced by a free energy functional derivative. The latter limit yields a mixed quantum-classical formulation which has previously been introduced by I. Burghardt and B. Bagchi, Chem. Phys. 134, 343 (2006).

Effective-mode representation of non-Markovian dynamics: a hierarchical approximation of the spectral density. II. Application to environment-induced nonadiabatic dynamics.

The non-Markovian approach developed in the companion paper [Hughes et al., J. Chem. Phys. 131, 024109 (2009)], which employs a hierarchical series of approximate spectral densities, is extended to the treatment of nonadiabatic dynamics of coupled electronic states. We focus on a spin-boson-type Hamiltonian including a subset of system vibrational modes which are treated without any approximation, while a set of bath modes is transformed to a chain of effective modes and treated in a reduced-dimensional space. Only the first member of the chain is coupled to the electronic subsystem. The chain construction can be truncated at successive orders and is terminated by a Markovian closure acting on the end of the chain. From this Mori-type construction, a hierarchy of approximate spectral densities is obtained which approach the true bath spectral density with increasing accuracy. Applications are presented for the dynamics of a vibronic subsystem comprising a high-frequency mode and interacting with a low-frequency bath. The bath is shown to have a striking effect on the nonadiabatic dynamics, which can be rationalized in the effective-mode picture. A reduced two-dimensional subspace is constructed which accounts for the essential features of the nonadiabatic process induced by the effective environmental mode. Electronic coherence is found to be preserved on the shortest time scale determined by the effective mode, while decoherence sets in on a longer time scale. Numerical simulations are carried out using either an explicit wave function representation of the system and overall bath or else an explicit representation of the system and effective-mode part in conjunction with a Caldeira-Leggett master equation.

Effective-mode representation of non-Markovian dynamics: a hierarchical approximation of the spectral density. I. Application to single surface dynamics.

An approach to non-Markovian system-environment dynamics is described which is based on the construction of a hierarchy of coupled effective environmental modes that is terminated by coupling the final member of the hierarchy to a Markovian bath. For an arbitrary environment, which is linearly coupled to the subsystem, the discretized spectral density is replaced by a series of approximate spectral densities involving an increasing number of effective modes. This series of approximants, which are constructed analytically in this paper, guarantees the accurate representation of the overall system-plus-bath dynamics up to increasing times. The hierarchical structure is manifested in the approximate spectral densities in the form of the imaginary part of a continued fraction similar to Mori theory. The results are described for cases where the hierarchy is truncated at the first-, second-, and third-order level. It is demonstrated that the results generated from a reduced density matrix equation of motion and large dimensional system-plus-bath wavepacket calculations are in excellent agreement. For the reduced density matrix calculations, the system and hierarchy of effective modes are treated explicitly and the effects of the bath on the final member of the hierarchy are described by the Caldeira-Leggett equation and its generalization to zero temperature.

Closure of quantum hydrodynamic moment equations.

The hydrodynamic formulation of mixed quantum states involves a hierarchy of coupled equations of motion for the momentum moments of the Wigner function. In this work a closure scheme for the hierarchy is developed. The closure scheme uses information contained in the lower known moments to expand the Wigner phase-space distribution function in a Gauss-Hermite orthonormal basis. The higher moment required to terminate the hierarchy is then easily obtained from the reconstructed approximate Wigner function by a straightforward integration over the momentum space. Application of the moment closure scheme is demonstrated for the dissipative and nondissipative dynamics of two different systems: (i) double-well potential, (ii) periodic potential.

A hybrid hydrodynamic-Liouvillian approach to mixed quantum-classical dynamics: application to tunneling in a double well.

The hybrid quantum-classical approach of Burghardt and Parlant [Burghardt, I.; Parlant, G. J. Chem. Phys. 2004, 120, 3055], referred to here as the quantum-classical moment (QCM) approach, is demonstrated for the dynamics of a quantum double well coupled to a classical harmonic coordinate. The approach combines the quantum hydrodynamic and classical Liouvillian representations by the construction of a particular type of moments (that is, partial hydrodynamic moments) whose evolution is determined by a hierarchy of coupled equations. For pure states, which are at the center of the present study, this hierarchy terminates at the first order. In the Lagrangian picture, the deterministic trajectories result in dynamics which is Hamiltonian in the classical subspace, while the projection onto the quantum subspace evolves under a generalized hydrodynamic force. Importantly, this force also depends upon the classical (Q, P) variables. The present application demonstrates the tunneling dynamics in both the Eulerian and Lagrangian representations. The method is exact if the classical subspace is harmonic, as is the case for the systems studied here.

Dissipative quantum phase space dynamics on dynamically adapting grids.

A moving grid approach to a dynamical study of dissipative systems is described. The dynamics are studied in phase space for the Caldeira-Leggett master equation. The grid movement is based on the principle of equidistribution and, by using a grid smoothing technique, the grid points trace a path that continuously adapts to reflect the dynamics of a phase-space distribution function. The technique is robust and allows accurate computations to be obtained for long propagation times. The effects of dissipation on the dynamics are studied and results are presented for systems subject to both periodic and nonperiodic multiminimum potential functions.

Trajectory approach to dissipative quantum phase space dynamics: Application to barrier scattering.

The Caldeira-Leggett master equation, expressed in Lindblad form, has been used in the numerical study of the effect of a thermal environment on the dynamics of the scattering of a wave packet from a repulsive Eckart barrier. The dynamics are studied in terms of phase space trajectories associated with the distribution function, W(q,p,t). The equations of motion for the trajectories include quantum terms that introduce nonlocality into the motion, which imply that an ensemble of correlated trajectories needs to be propagated. However, use of the derivative propagation method (DPM) allows each trajectory to be propagated individually. This is achieved by deriving equations of motion for the partial derivatives of W(q,p,t) that appear in the master equation. The effects of dissipation on the trajectories are studied and results are shown for the transmission probability. On short time scales, decoherence is demonstrated by a swelling of trajectories into momentum space. For a nondissipative system, a comparison is made of the DPM with the "exact" transmission probability calculated from a fixed grid calculation.