Complete Nuclear Permutation Inversion Invariant Artificial Neural Network (CNPI-ANN) Diabatization for the Accurate Treatment of Vibronic Coupling Problems

International audience; A recently developed scheme to produce accurate high-dimensional coupled diabatic potential energy surfaces (PESs) based on artificial neural networks (ANNs) [J. Chem. Phys. 2018, 149, 204106 and J. Chem. Phys. 2019, 151, 164118] is modified to account for the proper complete nuclear permutation inversion (CNPI) invariance. This new approach cures the problem intrinsic to the highly flexible ANN representation of diabatic PESs to account for the proper molecular symmetry accurately. It turns out that the use of CNPI invariants as coordinates for the input layer of the ANN leads to a much more compact and thus more efficient representation of the diabatic PES model without any loss of accuracy. In connection with a properly symmetrized vibronic coupling reference model, which is modified by the output neurons of the CNPI-ANN, the resulting adiabatic PESs show perfect symmetry and high accuracy. In the present paper, the new approach will be described and thoroughly tested. The test case is the representation and corresponding vibrational/vibronic nuclear dynamics of the low-lying electronic states of planar NO 3 for which a large number of ab initio data is available. Thus, the present results can be compared directly with the previous studies.