Viel Alexandra, Williams David M G, Eisfeld Wolfgang
University Rennes, CNRS, IPR (Institut de Physique de Rennes) - UMR 6251, F-35000 Rennes, FranceTheoretische Chemie, Universität Bielefeld, Postfach 100131, D-33501 Bielefeld, Germany.
Theoretische Chemie, Universität Bielefeld, Postfach 100131, D-33501 Bielefeld, Germany.
J Chem Phys. 2021 Feb 28;154(8):084302. doi: 10.1063/5.0039503.
The photodetachment spectrum of the nitrate anion (NO ) is simulated from first principles using wavepacket quantum dynamics propagation and a newly developed accurate full-dimensional fully coupled five state diabatic potential model. This model utilizes the recently proposed complete nuclear permutation inversion invariant artificial neural network diabatization technique [D. M. G. Williams and W. Eisfeld, J. Phys. Chem. A 124, 7608 (2020)]. The quantum dynamics simulations are designed such that temperature effects and the impact of near threshold detachment are taken into account. Thus, the two available experiments at high temperature and at cryogenic temperature using the slow electron velocity-map imaging technique can be reproduced in very good agreement. These results clearly show the relevance of hot bands and vibronic coupling between the X̃ A ground state and the B̃ E' excited state of the neutral radical. This together with the recent experiment at low temperature gives further support for the proper assignment of the ν fundamental, which has been debated for many years. An assignment of a not yet discussed hot band line is also proposed.
利用波包量子动力学传播和新开发的精确全维全耦合五态非绝热势模型，从第一性原理模拟了硝酸根阴离子（NO₃⁻）的光解离光谱。该模型采用了最近提出的完全核排列反转不变人工神经网络非绝热技术[D. M. G. Williams和W. Eisfeld，《物理化学杂志A》124, 7608 (2020)]。量子动力学模拟的设计考虑了温度效应和近阈值解离的影响。因此，可以很好地重现使用慢电子速度映射成像技术在高温和低温下进行的两个现有实验。这些结果清楚地表明了中性自由基的X̃ A₁基态和B̃ E'激发态之间的热带和振动电子耦合的相关性。这与最近在低温下进行的实验一起，进一步支持了多年来一直存在争议的ν₁基频的正确归属。还提出了一条尚未讨论的热带线的归属。
