1. Accurate quantum dynamics simulation of the photodetachment spectrum of the nitrate anion (NO3−) based on an artificial neural network diabatic potential model
- Author
-
Alexandra Viel, David M. G. Williams, Wolfgang Eisfeld, Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Theoretische Chemie, Universität Bielefeld, Germany, Universität Bielefeld = Bielefeld University, Ei375/6-2, Deutsche Forschungsgemeinschaft, 40442PD, PHC/DAAD Procope, and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Physics ,[PHYS]Physics [physics] ,010304 chemical physics ,Wave packet ,Quantum dynamics ,Diabatic ,Vibronic couplings ,General Physics and Astronomy ,Electron ,010402 general chemistry ,01 natural sciences ,Molecular physics ,Hot band ,0104 chemical sciences ,Vibronic coupling ,MCTDH ,Excited state ,0103 physical sciences ,Artificial Neuron Networks ANN ,Physical and Theoretical Chemistry ,Physics::Chemical Physics ,Ground state ,Spectroscopy - Abstract
International audience; The photodetachment spectrum of the nitrate anion (NO − 3) 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 theX 2 A ′ 2 ground state and theB 2 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 3 fundamental, which has been debated for many years. An assignment of a not yet discussed hot band line is also proposed.
- Published
- 2021