Optimization of Quantum Nuclei Positions with the Adaptive Nuclear-Electronic Orbital Approach.

The use of multicomponent methods has become increasingly popular over the last years. Under this framework, nuclei (commonly protons) are treated quantum mechanically on the same footing as the electronic structure problem. Under the use of atomic-centered orbitals, this can lead to some complications as the ideal location of the nuclear basis centers must be optimized. In this contribution, we propose a straightforward approach to determine the position of such centers within the self-consistent cycle of a multicomponent calculation, making use of individual proton charge centroids. We test the method on model systems including the water dimer, a protonated water tetramer, and a porphine system. Comparing to numerical gradient calculations, the adaptive nuclear-electronic orbital (NEO) procedure is able to converge the basis centers to within a few cents of an Ångström and with less than 0.1 kcal/mol differences in absolute energies. This is achieved in one single calculation and with a small added computational effort of up to 80% compared to a regular NEO- self-consistent field run. An example application for the human transketolase proton wire is also provided.