Department of Chemistry, University of Liège, B4000 Liège, Belgium.
Phys Chem Chem Phys. 2011 May 14;13(18):8331-44. doi: 10.1039/c1cp20094a. Epub 2011 Apr 12.
The attosecond time-scale electronic dynamics induced by an ultrashort laser pulse is computed using a multi configuration time dependent approach in ABCU (C(10)H(19)N), a medium size polyatomic molecule with a rigid cage geometry. The coupling between the electronic states induced by the strong pulse is included in the many electron Hamiltonian used to compute the electron dynamics. We show that it is possible to implement control of the electron density stereodynamics in this medium size molecule by varying the characteristics of the laser pulse, for example by polarizing the electric field either along the N-C axis of the cage, or in the plane perpendicular to it. The excitation produces an oscillatory, non-stationary, electronic state that exhibits localization of the electron density in different parts of the molecule both during and after the pulse. The coherent oscillations of the non-stationary electronic state are also demonstrated through the alternation of the dipole moment of the molecule.
采用多组态含时相关方法（ABCU，C(10)H(19)N）在阿秒时间尺度上计算超短激光脉冲诱导的电子动力学，ABCU 是一个中等大小的多原子分子，具有刚性笼状几何结构。强脉冲诱导的电子态之间的耦合包含在用于计算电子动力学的多电子哈密顿量中。我们表明，通过改变激光脉冲的特性，例如将电场沿笼的 N-C 轴或垂直于该轴的平面极化，有可能控制这种中等大小分子中的电子密度立体动力学。激发产生一个振荡的、非稳态的电子态，在脉冲期间和之后，电子密度在分子的不同部分定位。通过分子偶极矩的交替，也证明了非稳态电子态的相干振荡。
