Farnum John D, Gidofalvi Gergely, Mazziotti David A
Department of Chemistry, The University of Chicago, Chicago, IL 60637, USA.
J Chem Phys. 2006 Jun 21;124(23):234103. doi: 10.1063/1.2206585.
Understanding and modeling the interaction between light and matter is essential to the theory of optical molecular control. While the effect of the electric field on a molecule's electronic structure is often not included in control theory, it can be modeled in an optimal control algorithm by a set or toolkit of potential energy surfaces indexed by discrete values of the electric field strength where the surfaces are generated by Born-Oppenheimer electronic structure calculations that directly include the electric field. Using a new optimal control algorithm with a trigonometric mapping to limit the maximum field strength explicitly, we apply the surface-toolkit method to control the hydrogen fluoride molecule. Potential energy surfaces in the presence and absence of the electric field are created with two-electron reduced-density-matrix techniques. The population dynamics show that adjusting for changes in the electronic structure of the molecule beyond the static dipole approximation can be significant for designing a field that drives a realistic quantum system to its target observable.
理解并模拟光与物质之间的相互作用对于光学分子控制理论至关重要。虽然电场对分子电子结构的影响在控制理论中常常未被纳入，但可以在最优控制算法中通过一组由电场强度离散值索引的势能面或工具包来进行建模，其中这些势能面是由直接包含电场的玻恩 - 奥本海默电子结构计算生成的。使用一种新的带有三角函数映射以明确限制最大场强的最优控制算法，我们将表面工具包方法应用于控制氟化氢分子。利用双电子约化密度矩阵技术创建有电场和无电场情况下的势能面。布居动力学表明，针对分子电子结构变化进行调整，超越静态偶极近似对于设计一个能将实际量子系统驱动至其目标可观测量的场可能具有重要意义。
