Electronically nonadiabatic photodissociation can be investigated in detail by experiments. This provides an opportunity to validate the current theory of electronically nonadiabatic processes, but is great challenge because the time scale of photodissociation processes can be long compared to the current capability for accurate direct dynamics simulations. To circumvent this difficulty, we have been using analytic diabatic potential energy matrices, such that the simulation time scale can be extended to the nanosecond region without neglecting the effects of external electron correlation. In previous work, we have developed full-dimensional three-state potential energy matrices for thioanisole photodissociation. In the current work, we extend this work in two main ways: (i) we improve the treatment of the initial torsional potential, and (ii) we shift the potential energy surfaces to investigate the quantitative effect on the dissociation lifetimes and product branching ratios of changing the energy and location of the S₁–S₂ conical intersection.

电子非绝热光解离可以通过实验进行详细研究。这为验证电子非绝热过程的当前理论提供了机会，但是这是一个巨大的挑战，因为与当前用于精确直接动力学模拟的能力相比，光解离过程的时间尺度可能更长。为了避免这一困难，我们一直在使用解析非绝热势能矩阵，以便可以将仿真时标扩展到纳秒级区域，而不会忽略外部电子相关性的影响。在以前的工作中，我们已经开发了用于硫代苯甲醚光解离的全维三态势能矩阵。在目前的工作中，我们通过两种主要方式扩展这项工作：（i）我们改善对初始扭转潜力的治疗，₁ –S ₂圆锥形相交。