High-order geometric integrators for the local cubic variational Gaussian wavepacket dynamics
Gaussian wavepacket dynamics has proven to be a useful semiclassical approximation for quantum simulations of high-dimensional systems with low anharmonicity. Compared to Heller's original local harmonic method, the variational Gaussian wavepacket dynamics is more accurate, but much more difficult to apply in practice because it requires evaluating the expectation values of the potential energy, gradient, and Hessian. If the variational approach is applied to the local cubic approximation of the potential, these expectation values can be evaluated analytically, but they still require the costly third derivative of the potential. To reduce the cost of the resulting local cubic variational Gaussian wavepacket dynamics, we describe efficient high-order geometric integrators, which are symplectic, time-reversible, and norm-conserving. For small time steps, they also conserve the effective energy. We demonstrate the efficiency and geometric properties of these integrators numerically on a multidimensional, nonseparable coupled Morse potential.
WOS:001153167200006
2024-01-28
160
4
044113
REVIEWED
EPFL
| Funder | Grant Number |
Horizon 2020 Framework Programmehttps://doi.org/10.13039/100010661 | 683069-MOLEQULE |
European Research Council (ERC) under the European Union | |