Veintemillas David, Chang Bo Y, Sola Ignacio R
Departamento de Quimica Fisica, Universidad Complutense, Madrid 28040, Spain.
School of Chemistry, Seoul National University, Seoul 08826, Republic of Korea.
J Chem Theory Comput. 2025 Jul 8;21(13):6315-6324. doi: 10.1021/acs.jctc.5c00609. Epub 2025 Jun 20.
The yield of a photochemical process can be maximized by optimizing the driving fields, such as in optical control, or the initial wave function, as in geometrical optimization. We combine both algorithms in an iterative process, showing very fast convergence and great improvement in the yields, as applied to driving population to the second excited state of the molecular hydrogen cation through the first excited dissociative state by a pump-pump scheme. The results reveal the impact of the initial vibrational coherences in photoinduced processes that occur at nuclear configurations very far from the ground state, or that are even mediated by processes in the continuum. On the other hand, depending on whether we maximize the total electronic population (that mainly dissociates) or the bound population, the initial wave functions change considerably, involving nodal patterns in the position or in the momentum representations, respectively, that lead to different dynamics.
通过优化驱动场（如在光学控制中）或初始波函数（如在几何优化中），可以使光化学过程的产率最大化。我们在一个迭代过程中结合了这两种算法，结果表明，在通过泵浦-泵浦方案将分子氢阳离子的布居驱动到第一激发解离态进而到达第二激发态的过程中，该方法收敛速度极快，产率有显著提高。结果揭示了初始振动相干性在光诱导过程中的影响，这些过程发生在与基态相距甚远的核构型处，甚至由连续介质中的过程介导。另一方面，根据我们是使主要解离的总电子布居最大化还是使束缚布居最大化，初始波函数会发生相当大的变化，分别涉及位置或动量表象中的节点模式，这会导致不同的动力学。
