Variational nonadiabatic dynamics in the moving crude adiabatic representation: Further merging of nuclear dynamics and electronic structure
arXiv:1801.00703 · doi:10.1063/1.5020655
Abstract
A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new approach is elimination of any global or local model representation of electronic potential energy surfaces, instead, the electron-nuclear interaction is treated explicitly using the Gaussian integration. As a result, the new scheme does not introduce any uncontrolled approximations. The employed variational principle ensures the energy conservation and leaves the number of electronic and nuclear basis functions as the only parameter determining the accuracy. To assess performance of the approach, a model with two electronic and two nuclear spacial degrees of freedom containing conical intersections between potential energy surfaces has been considered. Dynamical features associated with nonadiabatic transitions and nontrivial geometric (or Berry) phases were successfully reproduced within a limited basis expansion.
arXiv commentJ. Chem. Phys. in press
References in corpus (2)
Cited by in corpus (7)
- Quasi-Diabatic Propagation Scheme for Simulating Polariton Chemistry
- Ab-initio Symmetric Quasi-Classical Approach to Investigate Molecular Tully Models
- Nonadiabatic Quantum Dynamics with Frozen-Width Gaussians
- Family of Gaussian wavepacket dynamics methods from the perspective of a nonlinear Schrödinger equation
- The moving crude adiabatic alternative to the adiabatic representation in excited state dynamics
- Local diabatic representation of conical intersection quantum dynamics
- Mixed quantum-classical approach to model non-adiabatic electron-nuclear dynamics: Detailed balance and improved surface hopping method