Theory and applications of fluctuating-charge models

Abstract

Fluctuating-charge models are computationally efficient methods of treating polarization and charge-transfer phenomena in molecular mechanics and classical molecular dynamics simulations. They are also theoretically appealing as they are minimally parameterized, with parameters corresponding to the chemically important concepts of electronegativities and chemical hardness. However, they are known to overestimate charge transfer for widely separated atoms, leading to qualitative errors in the predicted charge distribution and exaggerated electrostatic properties. We present the charge transfer with polarization current equilibration (QTPIE) model, which solves this problem by introducing distance-dependent electronegativities. A graph-theoretic analysis of the topology of charge transfer allows us to relate the fundamental quantities of charge transfer back to the more familiar variables that represent atomic partial charges. This allows us to formulate a unified theoretical framework for fluctuating-charge models and topological charge descriptors. We also demonstrate the important role of charge screening effects in obtaining correct size extensivity in electrostatic properties. Analyzing the spatial symmetries of these properties allows us to shed light on the role of charge conservation in the electronegativity equalization process. Finally, we develop a water model for use in classical molecular dynamics simulations that is capable of treating both polarization and charge transfer phenomena.