与随机相位和解：随机规范下的从头算锥形交叉动力学
Making peace with random phases: Ab initio conical intersection dynamics in random gauges
AI总结：
针对绝热电子态随机相位阻碍非绝热动力学建模的问题，本文提出随机规范局域透热表示，并通过二维 Shin-Metiu 模型验证其可实现精确的从头算锥形交叉动力学。
摘要：
锥形交叉动力学的从头算建模对于多种光化学、光物理和生物过程至关重要。然而，从电子结构计算获得的绝热电子态包含随机相位，或更一般地说，随机规范固定，这阻碍了非绝热分子动力学的建模。在此，我们开发了一种随机规范局域透热表示，它能够直接利用在电子结构计算过程中被随机赋予相位的绝热电子态，对锥形交叉动力学进行精确建模。通过在有无外磁场两种情况下对二维 Shin-Metiu 模型进行精确的从头算建模，证明了该方法的实用性。我们的结果提供了一种将电子结构计算整合到非绝热量子动力学中的简便途径，从而为锥形交叉动力学的从头算建模铺平了道路。
英文摘要：
Ab initio modeling of conical intersection dynamics is crucial for various photochemical, photophysical, and biological processes. However, adiabatic electronic states obtained from electronic structure computations involve random phases, or more generally, random gauge fixings, which hampers the modeling of nonadiabatic molecular dynamics. Here we develop a random-gauge local diabatic representation that allows an exact modeling of conical intersection dynamics directly using the adiabatic electronic states with phases randomly assigned during the electronic structure computations. Its utility is demonstrated by an exact ab initio modeling of the two-dimensional Shin-Metiu model with and without an external magnetic field. Our results provide a simple approach to integrating the electronic structure computations into non-adiabatic quantum dynamics, thus paving the way for ab initio modeling of conical intersection dynamics.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
