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The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat…
We present a new partially linearized mapping-based approach for approximating real-time quantum correlation functions in condensed-phase nonadiabatic systems, called spin-PLDM. Within a classical trajectory picture, partially linearized…
In the previous paper [J. R. Mannouch and J. O. Richardson, J.~Chem.~Phys.~xxx, xxxxx (xxxx)] we derived a new partially linearized mapping-based classical-trajectory technique, called spin-PLDM. This method describes the dynamics…
We extend the Mixed Quantum-Classical Initial Value Representation (MQC-IVR), a semiclassical method for computing real-time correlation functions, to electronically nonadiabatic systems using the Meyer-Miller-Stock-Thoss (MMST) Hamiltonian…
We propose a trajectory-based method for simulating nonadiabatic dynamics in molecular systems with two coupled electronic states. Employing a quantum-mechanically exact mapping of the two-level problem to a spin-1/2 coherent state, we…
The mapping approach addresses the mismatch between the continuous nuclear phase space and discrete electronic states by creating an extended, fully continuous phase space using a set of harmonic oscillators to encode the populations and…
Mixed quantum-classical mechanics descriptions are critical to modeling coupled electron-nuclear dynamics, i.e. non-adiabatic molecular dynamics, relevant to photochemical and photophysical processes. We argue that, for polyatomic…
We benchmark a set of quantum-chemistry methods, including multitrajectory Ehrenfest, fewest-switches surface-hopping, and multiconfigurational-Ehrenfest dynamics, against exact quantum-many-body techniques by studying real-time dynamics in…
The formalism of the generalized quantum master equation (GQME) is an effective tool to simultaneously increase the accuracy and the efficiency of quasiclassical trajectory methods in the simulation of nonadiabatic quantum dynamics. The…
This article investigates the weak approximation towards the invariant measure of semi-linear stochastic differential equations (SDEs) under non-globally Lipschitz coefficients. For this purpose, we propose a linear-theta-projected Euler…
The non-local nature of the correlations possessed by quantum systems may be revealed by experimental demonstrations of the violation of Bell-type inequalities. Recent work has placed bounds on the correlations that quantum systems can…
Simulating the nonadiabatic dynamics of condensed-phase systems continues to pose a significant challenge for quantum dynamics methods. Approaches based on sampling classical trajectories within the mapping formalism, such as the linearized…
We introduce a simple ansatz for the wavefunction of a many-body system based on coupled forward and backward-propagating semiclassical trajectories. This method is primarily aimed at, but not limited to, treating nonequilibrium dynamics in…
Ehrenfest dynamics is a useful approximation for ab initio mixed quantum-classical molecular dynamics that can treat electronically nonadiabatic effects. Although a severe approximation to the exact solution of the molecular time-dependent…
The theoretical development of quasi-Monte Carlo (QMC) methods for uncertainty quantification of partial differential equations (PDEs) is typically centered around simplified model problems such as elliptic PDEs subject to homogeneous zero…
We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations…
The accuracy of the noninteracting electron approximation is examined for a model of vibrationally coupled electron transport in single molecule junction. In the absence of electronic-vibrational coupling, steady state transport in this…
The atomistic resolution recently achieved by ultrafast spectroscopies demands corresponding theoretical advances. Real-time time-dependent density-functional theory (RT-TDDFT) with Ehrenfest dynamics offers an optimal trade-off between…
Quantum path interferences or resonances in multilevel dissipative quantum systems play an important and intriguing role in the transport processes of nanoscale systems. Many previous minimalistic models used to describe the quantum path…
Nonadiabatic molecular dynamics occur in a wide range of chemical reactions and femtochemistry experiments involving electronically excited states. These dynamics are hard to treat numerically as the system's complexity increases and it is…