Related papers: Detailed balance in mixed quantum-classical mappin…

Interest in vibrational polaritonic chemistry, where ground-state chemical kinetics are modified via confined optical modes in a cavity, has surged in recent years. Although models have been developed to understand cavity-modified…

We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum…

Nonadiabatic dynamical processes are one of the most important quantum mechanical phenomena in chemical, materials, biological, and environmental molecular systems, where the coupling between different electronic states is either inherent…

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…

Experiments indicate that collective coupling of molecular ensembles to confined optical modes can modify excited-state dynamics and photochemical reactivity. To describe such cavity-induced effects at atomic resolution, semi-classical…

Rare nonadiabatic events play a central role in photochemistry but remain difficult to simulate because excited-state dynamics is computationally demanding and often stochastic. Here we introduce a deterministic and time-reversible…

Fewest switches surface hopping (FSSH) is a well benchmarked dynamical method for simulating nonadiabatic systems. In particular, the literature shows that for the spin-Boson model Hamiltonian, FSSH with appropriate corrections usually…

Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. Here, we show that for nonadiabatic dynamics with two…

Simulating charged many-body systems has been a computational demanding task due to the long-range nature of electrostatic interaction. For the multi-scale model of electrolytes which combines the strengths of atomistic/continuum…

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…

This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum-classical methods. Specifically, an exact path integral…

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 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…

Starting from a microscopic description of weak system-bath interactions, we derive from first principles a quantum master equation that does not rely on the well-known rotating wave approximation. This includes generic many-body systems,…

Dynamics of large complex systems, such as relaxation towards equilibrium in classical statistical mechanics, often obeys a master equation. The equation significantly simplifies the complexities but describes essential information of…

Markovian master equations (formally known as quantum dynamical semigroups) can be used to describe the evolution of a quantum state $\rho$ when in contact with a memoryless thermal bath. This approach has had much success in describing the…

We present a detailed derivation and numerical tests of a new mixed quantum-classical scheme to deal with non-adiabatic processes. The method is presented as the zero-th order approximation to the exact coupled dynamics of electrons and…

In response to a community prediction challenge, we simulate the nonadiabatic dynamics of cyclobutanone using the mapping approach to surface hopping (MASH). We consider the first 500 fs of relaxation following photo-excitation to the S2…

The exact nuclear time-dependent potential energy surface arises from the exact decomposition of electronic and nuclear motion, recently presented in [A. Abedi, N. T. Maitra, and E. K. U. Gross, Phys. Rev. Lett. 105, 123002 (2010)]. Such…

In the study of non-adiabatic chemical processes such as photocatalysis and photosynthesis, non-adiabatic molecular dynamics (NAMD) is an indispensable theoretical tool, which requires precise potential energy surfaces (PESs) of ground and…