Schirò Marco, Eich Florian G, Agostini Federica
JEIP, USR 3573 CNRS, Collège de France, PSL Research University, 11 Place Marcelin Berthelot, 75321 Paris Cedex 05, France.
HQS Quantum Simulations GmbH, Haid-und-Neu-Straße 7, D-76131 Karlsruhe, Germany.
J Chem Phys. 2021 Mar 21;154(11):114101. doi: 10.1063/5.0043790.
We develop a trajectory-based approach for excited-state molecular dynamics simulations of systems subject to an external periodic drive. We combine the exact-factorization formalism, allowing us to treat electron-nuclear systems in nonadiabatic regimes, with the Floquet formalism for time-periodic processes. The theory is developed starting with the molecular time-dependent Schrödinger equation with the inclusion of an external periodic drive that couples to the system dipole moment. With the support of the Floquet formalism, quantum dynamics is approximated by combining classical-like, trajectory-based, nuclear evolution with electronic dynamics represented in the Floquet basis. The resulting algorithm, which is an extension of the coupled-trajectory mixed quantum-classical scheme for periodically driven systems, is applied to a model study, exactly solvable, with different field intensities.
我们开发了一种基于轨迹的方法，用于对受外部周期性驱动的系统进行激发态分子动力学模拟。我们将精确因子分解形式（使我们能够在非绝热区域处理电子 - 核系统）与用于时间周期性过程的弗洛凯形式相结合。该理论从包含与系统偶极矩耦合的外部周期性驱动的分子含时薛定谔方程出发进行发展。在弗洛凯形式的支持下，通过将类经典的、基于轨迹的核演化与弗洛凯基表示的电子动力学相结合，对量子动力学进行近似。所得算法是用于周期性驱动系统的耦合轨迹混合量子 - 经典方案的扩展，被应用于一个具有不同场强且可精确求解的模型研究。
