Machine learning configuration interaction for ab initio potential energy curves

The concept of machine learning configuration interaction (MLCI) (J. Chem. Theory Comput. 2018, 14, 5739), where an artificial neural network (ANN) learns on the fly to select important configurations, is further developed so that accurate ab initio potential energy curves can be efficiently calculated. This development includes employing the artificial neural network also as a hash function for the efficient deletion of duplicates on the fly so that the single and double space does not need to be stored and this barrier to scalability is removed. In addition, configuration state functions are introduced into the approach so that pure spin states are guaranteed, and the transferability of data between geometries is exploited. This improved approach is demonstrated on potential energy curves for the nitrogen molecule, water, and carbon monoxide. The results are compared with full configuration interaction values, when available, and different transfer protocols are investigated. It is shown that, for all of the considered systems, accurate potential energy curves can now be efficiently computed with MLCI. For the potential curves of N2 and CO, MLCI can achieve lower errors than stochastically selecting configurations while also using substantially less processor hours.