Calculating Vibrational Excited State Absorptions with Excited State Constrained Minimized Energy Surfaces
Calculating Vibrational Excited State Absorptions with Excited State Constrained Minimized Energy Surfaces
复制标题
使用激发态约束最小化能量面计算振动激发态吸收
DOI：
10.1021/acs.jpca.3c01420
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Yang, Yang
中科院分区：
文献类型：
--
作者：
Wang, Yiwen;Chen, Zehua;Yang, Yang
振动光谱的建模和解释对于利用振动光谱研究反应动力学至关重要。大多数先前的理论发展集中于描述基本的振动跃迁，而较少的发展集中于振动激发态吸收。在这项研究中，我们提出了一种使用激发态约束最小能量面（CMES）来描述振动激发态吸收的新方法。激发态 CMES 的获得与我们小组之前的基态 CMES 开发类似，但具有额外的波函数正交约束。使用一系列模型系统，包括谐振子、莫尔斯势、双阱势、四次势和二维非简势，我们证明了这种新程序可以很好地估计振动激发态吸收的过渡频率。这些结果明显优于使用传统势能面通过谐波近似获得的结果，证明了基于激发态 CMES 的方法在计算实际系统中振动激发态吸收方面的前景。
The modeling and interpretation of vibrational spectra are crucial for studying reaction dynamics using vibrational spectroscopy. Most prior theoretical developments focused on describing fundamental vibrational transitions while fewer developments focused on vibrational excited state absorptions. In this study, we present a new method that uses excited state constrained minimized energy surfaces (CMESs) to describe vibrational excited state absorptions. The excited state CMESs are obtained similarly to the previous ground state CMES development in our group but with additional wave function orthogonality constraints. Using a series of model systems, including the harmonic oscillator, Morse potential, double-well potential, quartic potential, and two-dimensional anharmonic potential, we demonstrate that this new procedure provides good estimations of the transition frequencies for vibrational excited state absorptions. These results are significantly better than those obtained from harmonic approximations using conventional potential energy surfaces, demonstrating the promise of excited state CMES-based methods for calculating vibrational excited state absorptions in real systems.