Sola Ignacio R, García-Vela Alberto
Departamento de Química Física, Universidad Complutense de Madrid (y Unidad Asociada I+D+i CSIC), Madrid 28040, Spain.
Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano, 123, Madrid 28006, Spain.
J Chem Theory Comput. 2025 Aug 12;21(15):7267-7278. doi: 10.1021/acs.jctc.5c00655. Epub 2025 Jul 30.
We derive and apply the geometric optimization methodology to modify the photodissociation spectra of CHI in the A band. For this purpose, we prepare optimized initial wave functions that maximally exploit interference-induced coherent control to drive a reaction mediated by nonadiabatic couplings in a polyatomic molecule essentially from the beginning. By designing functionals that maximize the output of the products, or that imply competition between the products, or discrimination of one of them, we test the performance of the methods and the effect of preparing initial vibrational coherences among CH-I stretching vibrational states, CH vibrational states, or both. Our results show that using weak ultrashort pulses, one can easily increase the efficiency of the reaction toward any of the products by 100-200% using vibrational states related to the reaction coordinate; that one can increase the efficiency by more than 100% and at the same time almost completely quench the output of products in the other channels. Finally, if one demands high selectivity in the reaction, we show that it is possible to suppress even the most dominant channel to less than one part in a million by preparing superpositions of all available vibrational states optimized with the proper functional.
我们推导并应用几何优化方法来修改CHI在A波段的光解离光谱。为此，我们准备了优化的初始波函数，该波函数从本质上最大程度地利用干涉诱导的相干控制来驱动多原子分子中非绝热耦合介导的反应。通过设计能使产物输出最大化、暗示产物之间存在竞争或区分其中一种产物的泛函，我们测试了这些方法的性能以及在CH-I伸缩振动状态、CH振动状态或两者之间制备初始振动相干的效果。我们的结果表明，使用弱超短脉冲，利用与反应坐标相关的振动状态，可轻松将朝向任何一种产物的反应效率提高100% - 200%；可将效率提高100%以上，同时几乎完全抑制其他通道中产物的输出。最后，如果要求反应具有高选择性，我们表明通过制备用适当泛函优化的所有可用振动状态的叠加，有可能将最主要的通道抑制到百万分之一以下。
