Nonvariational time-dependent multiconfiguration self-consistent field equations for electronic dynamics in laser-driven molecules.
Nonvariational time-dependent multiconfiguration self-consistent field equations for electronic dynamics in laser-driven molecules.
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激光驱动分子电子动力学的非变分时间相关多构型自洽场方程。
DOI：
10.1063/1.2774979
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发表时间：
2007
期刊：
影响因子：
--
通讯作者：
F. Dion
中科院分区：
文献类型：
--
作者：
T. Nguyen;M. Peters;Sen;E. Sinelnikov;F. Dion
开发了一种瞬态多构型自洽场 (TDMCSCF) 方案，用于描述激光驱动的多电子原子或分子系统的时间分辨电子动力学，直接从系统的瞬态薛定谔方程开始。这种非变分公式旨在充分利用现有的、成熟的量子化学 MCSCF 代码的概念、工具和设施。该理论特别使用了依赖于时间的构型混合和轨道变换的酉表示。在短时或绝热近似内，TDMCSCF 方案相当于二阶分裂算子算法，通常涉及时间相关电子哈密顿量的两个非对易单电子和双电子部分。我们实施该方案来计算在最小基础内描述的双电子 H2 分子的激光诱导动力学，并展示电子相关性如何受到分子与强激光场相互作用的影响。
A time-dependent multiconfiguration self-consistent field (TDMCSCF) scheme is developed to describe the time-resolved electron dynamics of a laser-driven many-electron atomic or molecular system, starting directly from the time-dependent Schrodinger equation for the system. This nonvariational formulation aims at the full exploitations of concepts, tools, and facilities of existing, well-developed quantum chemical MCSCF codes. The theory uses, in particular, a unitary representation of time-dependent configuration mixings and orbital transformations. Within a short-time, or adiabatic approximation, the TDMCSCF scheme amounts to a second-order split-operator algorithm involving generically the two noncommuting one-electron and two-electron parts of the time-dependent electronic Hamiltonian. We implement the scheme to calculate the laser-induced dynamics of the two-electron H2 molecule described within a minimal basis, and show how electron correlation is affected by the interaction of the molecule with a strong laser field.
影响因子：
3.3
作者：
Li, XS;Smith, SM;Schlegel, HB
通讯作者：
Schlegel, HB