A unified theoretical framework for fluctuating-charge models in atom-space and in bond-space.
Our previously introduced QTPIE (charge transfer with polarization current equilibration) model [J. Chen and T. J. Martínez, Chem. Phys. Lett. 438, 315 (2007)] is a fluctuating-charge model with correct asymptotic behavior. Unlike most other fluctuating-charge models, QTPIE is formulated in terms of charge-transfer variables and pairwise electronegativities, not atomic charge variables and electronegativities. The pairwise character of the electronegativities in QTPIE allows us to avoid spurious charge transfer when bonds are broken. However, the increased number of variables leads to considerable computational expense and a rank-deficient set of working equations, which is numerically inconvenient. Here, we show that QTPIE can be exactly reformulated in terms of atomic charge variables, leading to a considerable reduction in computational complexity. The transformation between atomic and bond variables is generally applicable to arbitrary fluctuating charge models and uncovers an underlying topological framework that can be used to understand the relation between fluctuating-charge models and the classical theory of electrical circuits.
Chen
Jiahao
J
Department of Chemistry, Frederick Seitz Materials Research Laboratory and The Beckman Institute, University of Illinois at Urbana Champaign, Urbana, Illinois 61801, USA.
Hundertmark
Dirk
D
Martínez
Todd J
TJ