Adaptive molecular decomposition: large-scale quantum chemistry for liquids

J Chem Phys. 2013 Mar 14;138(10):104108. doi: 10.1063/1.4793708.

Abstract

We present a linear-scaling method based on self-consistent charge non-orthogonal tight-binding. Linear scaling is achieved using a many-body expansion, which is adjusted dynamically to the instantaneous molecular configuration of a liquid. The method is capable of simulating liquids over large length and time scales, and also handles reactions correctly. Benchmarking on typical carbonate electrolytes used in Li-ion batteries displays excellent agreement with results from full tight-binding calculations. The decomposition slightly breaks the Hellmann-Feynman theorem, which is demonstrated by application to water. However, an additional correction also enables dynamical simulation in this case.