Bridging the 12-6-4 Model and the Fluctuating Charge Model

Authors

Pengfei LiFollow

Document Type

Article

Publication Date

Summer 7-22-2021

Publication Title

Frontiers in Chemistry

Volume

9

Issue

721960

Pages

1-9

Publisher Name

Frontiers Media SA

Publisher Location

Lausanne, Switzerland

Abstract

Metal ions play important roles in various biological systems. Molecular dynamics (MD) using classical force field has become a popular research tool to study biological systems at the atomic level. However, meaningful MD simulations require reliable models and parameters. Previously we showed that the 12-6 Lennard-Jones nonbonded model for ions could not reproduce the experimental hydration free energy (HFE) and ion-oxygen distance (IOD) values simultaneously when ion has a charge of +2 or higher. We discussed that this deficiency arises from the overlook of the ion-induced dipole interaction in the 12-6 model, and this term is proportional to 1/r⁴ based on theory. Hence, we developed the 12- 6-4 model and showed it could solve this deficiency in a physically meaningful way. However, our previous research also found that the 12-6-4 model overestimated the coordination numbers (CNs) for some highly charged metal ions. And we attributed this artifact to that the current 12-6-4 scheme lacks a correction for the interactions among the first solvation shell water molecules. In the present study, we considered the ion-included dipole interaction by using the 12-6 model with adjusting the atomic charges of the first solvation shell water molecules. This strategy not only considers the ion-induced dipole interaction between ion and the first solvation shell water molecules but also well accounts for the increased repulsion among these water molecules compared to the bulk water molecules. We showed this strategy could well reproduce the experimental HFE and IOD values for Mg²⁺, Zn²⁺, Al³⁺, Fe³⁺, and In³⁺ and solve the CN overestimation issue of the 12-6-4 model for Fe³⁺ and In³⁺. Moreover, our simulation results showed good agreement with previous ab initio MD simulations. In addition, we derived the physical relationship between the C₄ parameter and induced dipole moment, which agreed well with our simulation results. Finally, we discussed the implications of the present work for simulating metalloproteins. Due to the fluctuating charge model uses a similar concept to the 12-6 model with adjusting atomic charges, we believe the present study builds a bridge between the 12-6-4 model and the fluctuating charge model.

Comments

Author Posting © Li, 2021. This article is posted here by permission of Li for personal use, not for redistribution. The article was published in Frontiers in Chemistry, Volume 9, July 2021, https://doi.org/10.3389/fchem.2021.721960

Recommended Citation

Li, P. (2021) Bridging the 12-6-4 Model and the Fluctuating Charge Model. Front. Chem. 9:721960. DOI: 10.3389/fchem.2021.721960

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This work is licensed under a Creative Commons Attribution 4.0 International License.

Copyright Statement

Copyright © 2021 Pengfei Li. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.