N-H photodissociation dynamics of electronically excited aniline: A three dimensional time-dependent quantum wavepacket study

We have simulated the dynamics of 1πσ* state-mediated nonadiabatic N-H bond dissociation in photo-excited aniline (C6H5NH2). A three-electronic state diabatic model potential, involving the ground, 1ππ*, and 1πσ* diabatic states,...

Quasi Diabatic Propagation Scheme for Direct Simulation of Proton-Coupled Electron Transfer Reaction

We apply a recently-developed quasi-diabatic (QD) propagation scheme to simulate proton-coupled electron transfer (PCET) reactions. This scheme enables a direct interface between an accurate diabatic dynamics approach and the adiabatic vibronic states. It explicitly avoids theoretical efforts to pre-construct diabatic states for the transferring electron and proton or reformulate diabatic dynamics methods to the adiabatic representation, both of which are non-trivial tasks. Using partial linearized path-integral approach and symmetrical quasi-classical approach as the diabatic dynamics methods, we demonstrate that the QD propagation scheme provides accurate vibronic dynamics of PCET reactions and reliably predict the correct reaction mechanism without any a priori assumptions. This work demonstrates the possibility to directly simulate challenging PCET reactions by using accurate diabatic dynamics approaches and adiabatic vibronic information.

Quasi Diabatic Propagation Scheme for Direct Simulation of Proton-Coupled Electron Transfer Reaction

We apply a recently-developed quasi-diabatic (QD) propagation scheme to simulate proton-coupled electron transfer (PCET) reactions. This scheme enables a direct interface between an accurate diabatic dynamics approach and the adiabatic vibronic states. It explicitly avoids theoretical efforts to pre-construct diabatic states for the transferring electron and proton or reformulate diabatic dynamics methods to the adiabatic representation, both of which are non-trivial tasks. Using partial linearized path-integral approach and symmetrical quasi-classical approach as the diabatic dynamics methods, we demonstrate that the QD propagation scheme provides accurate vibronic dynamics of PCET reactions and reliably predict the correct reaction mechanism without any a priori assumptions. This work demonstrates the possibility to directly simulate challenging PCET reactions by using accurate diabatic dynamics approaches and adiabatic vibronic information.

Approximate DFT-based methods for generating diabatic states and calculating electronic couplings: models of two and more states

Four types of density functional theory (DFT)-based approaches are assessed in this work for the approximate construction of diabatic states and evaluation of the electronic couplings between these states.

Quantum dynamics intervened by repeated nonselective measurements

We derive the theory of open quantum system dynamics intervened by a series of nonselective measurements. We analyze the cases of time-independent and time-dependent Hamiltonian dynamics between the measurements and find the approximate master equation in the stroboscopic limit. We also consider a situation, in which the measurement basis changes in time, and illustrate it by nonselective measurements in the basis of diabatic states of the Landau–Zener model.

Constrained subsystem density functional theory

Constrained Subsystem Density Fucntional Theory (CSDFT) allows to compute diabatic states for charge transfer reactions using the machinery of the constrained DFT method, and at the same time is able to embed such diabatic states in a molecular environment via a subsystem DFT scheme.