Laboratoire de Chimie Physique, Université Paris-Sud and CNRS, UMR 8000, F-91405 Orsay, France.
J Phys Chem A. 2012 Nov 26;116(46):11273-82. doi: 10.1021/jp305274y. Epub 2012 Sep 14.
In this work, we present optimal control calculations in a dissipative environment. To this end, the auxiliary density matrix method describing the dissipative quantum dynamics is combined with optimal control theory. The resulting approach, which is nonperturbative in the laser-system interaction, is applied to model the control of Cope's isomerization of the methyl-cyclopentadienylcarboxylate dimer, described as the motion along a one-dimensional reaction path. The construction of the reaction path model as well as the dipole moments required for the laser interaction are obtained from DFT quantum chemistry calculations. As a main result, we show that the proposed methodology, which includes the environment at the design stage of the control, leads to control fields which can react on dissipative effects during the dynamics and lead to an increased control objective, as compared to control fields obtained without dissipation. The chosen example is analyzed in detail, and the physical mechanisms of the control under dissipation are elucidated.
在这项工作中，我们在耗散环境中进行了最优控制计算。为此，我们将描述耗散量子动力学的辅助密度矩阵方法与最优控制理论相结合。这种方法对激光-系统相互作用是非微扰的，应用于模型化控制甲撑环戊二烯基羧酸甲酯二聚体的 Cope 异构化，其描述为沿一维反应路径的运动。反应路径模型的构建以及激光相互作用所需的偶极矩是从 DFT 量子化学计算中获得的。作为主要结果，我们表明，所提出的方法包括在控制设计阶段的环境，导致控制场可以在动力学过程中对耗散效应做出反应，并导致与没有耗散时获得的控制场相比，控制目标增加。选择的例子进行了详细分析，并阐明了耗散下控制的物理机制。
