Theoretical analysis of the S2←S0 vibronic spectrum of the 2-pyridone dimer.
Theoretical analysis of the S2←S0 vibronic spectrum of the 2-pyridone dimer.
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DOI：
10.1063/1.4939522
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发表时间：
2016-01
期刊：
影响因子：
--
通讯作者：
Sabine Kopec;H. Köppel
中科院分区：
文献类型：
--
作者：
Sabine Kopec;H. Köppel
氢键分子二聚体中激子和电子振动耦合之间的相互作用导致了复杂的光谱结构和其他有趣的现象，如激子能量分裂的淬灭。最近，我们扩展我们的分析，从猝灭机制的理论研究的完整的邻氰基苯酚二聚体的振动光谱。我们现在将同样的方法应用于2-吡啶酮二聚体的电子振动光谱，并讨论电子振动线的分配，以深入了解潜在的耦合机制。这是基于在RI-CC 2/aug-cc-pVTZ水平下获得的势能面。他们被用于动态分析的框架中的多模振动耦合方法。基于二次电子振动耦合模型的理论结果与实验共振双光子电离谱符合得很好。
The interplay between excitonic and vibronic coupling in hydrogen-bonded molecular dimers leads to complex spectral structures and other intriguing phenomena such as a quenching of the excitonic energy splitting. We recently extended our analysis from that of the quenching mechanism to the theoretical investigation of the complete vibronic spectrum for the ortho-cyanophenol dimer. We now apply the same approach to the vibronic spectrum of the 2-pyridone dimer and discuss the assignment of vibronic lines to gain insight into the underlying coupling mechanism. This is based on potential energy surfaces obtained at the RI-CC2/aug-cc-pVTZ level. They are used for the dynamical analysis in the framework of a multi-mode vibronic coupling approach. The theoretical results based on the quadratic vibronic coupling model are found to be in good agreement with the experimental resonant two-photon ionization spectrum.