Compact Bases for Vibronic Coupling in Spectral Simulations: The Photoelectron Spectrum of Cyclopentoxide in the Full 39 Internal Modes
Compact Bases for Vibronic Coupling in Spectral Simulations: The Photoelectron Spectrum of Cyclopentoxide in the Full 39 Internal Modes
复制标题
光谱模拟中振动耦合的紧凑基础：完整 39 种内模态环戊氧化物的光电子能谱
DOI：
10.1021/acs.jpclett.0c02199
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Yarkony, David
中科院分区：
文献类型：
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作者：
Shen, Yifan;Yarkony, David
我们报告了一种自动生成紧凑多模振动基的算法，用于中等大小分子的光谱模拟中Köppel-Domcke-Cederbaum （KDC）振动耦合波函数。作为全量子方法，振动膨胀的大小与振动模式的数量呈指数增长，因此中等大小的系统需要紧凑的基。产生这样一个基的问题包括两个部分：一个是选择振动的正常模式，另一个是每个模式中允许的声子的数量。先前开发的最终状态偏差技术解决了前一部分，而本研究的重点是后一部分：提出一种生成最佳声子分布的算法。利用这种声子分布，可以为15个原子量级的系统自动生成紧凑且价格合理的碱基。我们的算法被应用于确定环五氧化物在全部39个内模下的非绝热光电子能谱。
We report an algorithm to automatically generate compact multimode vibrational bases for the Köppel–Domcke–Cederbaum (KDC) vibronic coupling wave function used in spectral simulations of moderate-sized molecules. As a full quantum method, the size of the vibronic expansion grows exponentially with respect to the number of vibrational modes, necessitating compact bases for moderate-sized systems. The problem of generating such a basis consists of two parts: one is the choice of vibrational normal modes, and the other is the number of phonons allowed in each mode. A previously developed final-state-biased technique addresses the former part, and this work focuses on the latter part: proposing an algorithm for generating an optimal phonon distribution. By virtue of this phonon distribution, compact and affordable bases can be automatically generated for systems with on the order of 15 atoms. Our algorithm is applied to determine the nonadiabatic photoelectron spectrum of cyclopentoxide in the full 39 internal modes.