Center for Computational Natural Sciences and Bioinformatics, International institute of Information Technology, Hyderabad 500032, India.
J Chem Phys. 2010 Nov 7;133(17):174103. doi: 10.1063/1.3494543.
Optimal control theory is used to design a laser pulse for the multiphoton dissociation of the Fe-CO bond in the CO-heme compounds. The study uses a hexacoordinated iron-porphyrin-imidazole-CO complex in its ground electronic state as a model for CO liganded to the heme group. The potential energy and dipole moment surfaces for the interaction of the CO ligand with the heme group are calculated using density functional theory. Optimal control theory, combined with a time-dependent quantum dynamical treatment of the laser-molecule interaction, is then used to design a laser pulse capable of efficiently dissociating the CO-heme complex model. The genetic algorithm method is used within the mathematical framework of optimal control theory to perform the optimization process. This method provides good control over the parameters of the laser pulse, allowing optimized pulses with simple time and frequency structures to be designed. The dependence of photodissociation yield on the choice of initial vibrational state and of initial laser field parameters is also investigated. The current work uses a reduced dimensionality model in which only the Fe-C and C-O stretching coordinates are explicitly taken into account in the time-dependent quantum dynamical calculations. The limitations arising from this are discussed in Sec. IV.
最优控制理论被用于设计一个激光脉冲，以实现 CO-heme 化合物中 Fe-CO 键的多光子解离。该研究使用六配位铁卟啉-咪唑-CO 配合物在其基态电子态下作为模型，用于与血红素基团配位的 CO。使用密度泛函理论计算 CO 配体与血红素基团相互作用的势能和偶极矩表面。然后，最优控制理论与激光-分子相互作用的时间相关量子动力学处理相结合，用于设计能够有效解离 CO-heme 配合物模型的激光脉冲。遗传算法方法在最优控制理论的数学框架内用于执行优化过程。该方法可以很好地控制激光脉冲的参数，允许设计具有简单时间和频率结构的优化脉冲。还研究了光解产量对初始振动状态和初始激光场参数选择的依赖性。当前的工作使用了一个降维模型，其中仅在时间相关量子动力学计算中明确考虑了 Fe-C 和 C-O 伸缩坐标。在第 IV 节中讨论了由此产生的限制。
