Generalized Method for Charge-Transfer Equilibration in Reactive Molecular Dynamics

T Gergs and F Schmidt and T Mussenbrock and J Trieschmann, JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 17, 6691-6704 (2021).

DOI: 10.1021/acs.jctc.1c00382

Variable charge models (e.g., electronegativity equalization method (EEM), charge equilibration (QEq), electrostatic plus (ES+)) used in reactive molecular dynamics simulations often inherently impose a global charge transfer between atoms (approximating each system as an ideal metal). Consequently, most surface processes (e.g., adsorption, desorption, deposition, sputtering) are affected, potentially causing dubious dynamics. This issue has been addressed by certain split charge variants (i.e., split charge equilibration (SQE), redoxSQE) through a distance-dependent bond hardness, by the atomic charge ACKS2 and QTPIE models, which are based on the Kohn-Sham density functional theory, as well as by an electronegativity screening extension to the QEq model (approximating each system as an ideal insulator). In a brief review of the QEq and the QTPIE model, their applicability for studying surface interactions is assessed in this work. Following this evaluation, a revised generalization of the QEq and QTPIE models is proposed and formulated, called the charge-transfer equilibration model or in short the QTE model. This method is based on the equilibration of charge- transfer variables, which locally constrain the split charge transfer per unit time (i.e., due to overlapping orbitals) without any kind of bond hardness specification. Furthermore, a formalism relying solely on atomic charges is obtained by a respective transformation, employing an extended Lagrangian method. We moreover propose a mirror boundary condition and its implementation to accelerate surface investigations. The models proposed in this work facilitate reactive molecular dynamics simulations, which describe various materials and surface phenomena appropriately.

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