Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction
Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction
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DOI：
10.1063/1.4745836
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发表时间：
2012-12-14
影响因子：
4.4
通讯作者：
Gross, E. K. U.
中科院分区：
文献类型：
--
作者：
Abedi, Ali;Maitra, Neepa T.;Gross, E. K. U.
最近显示[A. Abedi，N.T. Maitra 和 E.K.U. Gross，物理学家。莱特牧师。 105, 123002 (2010)] 电子和原子核系统在依赖于时间的外部势中演化的完整波函数可以精确地分解为电子波函数和核波函数。精确的时间相关势能面（TDPES）和精确的时间相关矢量势的概念自然地从形式主义中出现。在这里，我们提出了形式主义的详细描述，包括电子和核波函数满足的方程的完整推导。我们证明了这种精确因式分解与传统玻恩-奥本海默展开式的关系。激光场中 H-2(+) 分子的一维模型显示了精确 TDPES 在解释耦合电子-核动力学方面的有用性：我们展示了其结构特征如何表明解离机制。我们将精确的 TDPES 与依赖时间的 Hartree 方法的势能面进行比较，并将传统的 Ehrenfest 动力学与精确 TDPES 上的 Ehrenfest 动力学进行比较。 (C) 2012 年美国物理研究所。 [http://dx.doi.org/10.1063/1.4745836]
It was recently shown [A. Abedi, N. T. Maitra, and E. K. U. Gross, Phys. Rev. Lett. 105, 123002 ( 2010)] that the complete wavefunction for a system of electrons and nuclei evolving in a time-dependent external potential can be exactly factorized into an electronic wavefunction and a nuclear wavefunction. The concepts of an exact time-dependent potential energy surface (TDPES) and exact time-dependent vector potential emerge naturally from the formalism. Here, we present a detailed description of the formalism, including a full derivation of the equations that the electronic and nuclear wavefunctions satisfy. We demonstrate the relationship of this exact factorization to the traditional Born-Oppenheimer expansion. A one-dimensional model of the H-2(+) molecule in a laser field shows the usefulness of the exact TDPES in interpreting coupled electron-nuclear dynamics: we show how features of its structure indicate the mechanism of dissociation. We compare the exact TDPES with potential energy surfaces from the time-dependent Hartree-approach, and also compare traditional Ehrenfest dynamics with Ehrenfest dynamics on the exact TDPES. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4745836]