Reparameterization of the chemical-potential equalization model with DFTB3: A practical balance between accuracy and transferability.

Abstract

To improve the performance of the third-order density-functional tight-binding method (DFTB3) for non-covalent interactions involving organic and biological molecules, a chemical-potential equalization (CPE) approach was introduced [J. Phys. Chem. A, 116, 9131 (2012)] and parameterized for the H, C, N, O, and S chemical elements [J. Chem. Phys., 143, 084123 (2015)]. Based largely on equilibrium structures, the parameterized DFTB3/CPE models were shown to exhibit improvements in molecular polarizabilities and intermolecular interactions. With more extensive analyses, however, we observe here that the available DFTB3/CPE models have two critical limitations: (1) they lead to sharply varying potential energy surfaces, thus causing numerical instability in molecular dynamics (MD) simulations, and (2) they lead to spurious interactions at short distances for some dimer complexes. These shortcomings are attributed to the employed screening functions and the overfitting of CPE parameters. In this work, we introduce a new strategy to simplify the parameterization procedure and significantly reduce free parameters down to four global (i.e., independent of element type) ones. With this strategy, two new models, DFTB3/CPE(r) and DFTB3/CPE(r†) are parameterized. The new models lead to smooth potential energy surfaces, stable MD simulations, and alleviate the spurious interactions at short distances, thus representing consistent improvements for both neutral and ionic hydrogen bonds.