Generalized discrete truncated Wigner approximation for nonadiabatic quantum-classical dynamics

Quantum-Classical Nonadiabatic Dynamics: Coupled- vs Independent-Trajectory Methods.

Trajectory-based mixed quantum-classical approaches to coupled electron-nuclear dynamics suffer from well-studied problems such as the lack of (or incorrect account for) decoherence in the trajectory surface hopping method and the inability of reproducing the spatial splitting of a nuclear wave packet in Ehrenfest-like dynamics. In the context of electronic nonadiabatic processes, these problem...

Quantum-classical Liouville dynamics of nonadiabatic proton transfer.

A proton transfer reaction in a linear hydrogen-bonded complex dissolved in a polar solvent is studied using mixed quantum-classical Liouville dynamics. In this system, the proton is treated quantum mechanically and the remainder of the degrees of freedom is treated classically. The rates and mechanisms of the reaction are investigated using both adiabatic and nonadiabatic molecular dynamics. W...

Nonadiabatic quantum-classical reaction rates with quantum equilibrium structure.

Time correlation function expressions for quantum reaction-rate coefficients are computed in a quantum-classical limit. This form for the correlation function retains the full quantum equilibrium structure of the system in the spectral density function but approximates the time evolution of the operator by quantum-classical Liouville dynamics. Approximate analytical expressions for the spectral...

Semiclassical Nonadiabatic Dynamics with Quantum Trajectories

Nonadiabatic processes involving quantum-like and classical-like coordinates with applications to nonadiabatic electron transfers

Nonadiabatic processes may involve both classical-like and quantum-like coordinates. A semiclassical analysis is used to treat the contribution of the former to the Franck-Condon factor in the reaction rate expression, thereby avoiding the usual harmonic oscillator approximation. Microcanonical and canonical rate constants are calculated, yielding an expression which includes contributions from...