Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published December 6, 2018 | Supplemental Material
Journal Article Open

The Polarizable Charge Equilibration Model for Transition-Metal Elements

Abstract

The polarizable charge equilibration (PQEq) method was developed to provide a simple but accurate description of the electrostatic interactions and polarization effects in materials. Previously, we optimized four parameters per element for the main group elements. Here, we extend this optimization to the 24 d-block transition-metal (TM) elements, columns 4–11 of the periodic table including Ti–Cu, Zr–Ag, and Hf–Au. We validate the PQEq description for these elements by comparing to interaction energies computed by quantum mechanics (QM). Because many materials applications involving TM are for oxides and other compounds that formally oxidize the metal, we consider a variety of oxidation states in 24 different molecular clusters. In each case, we compare interaction energies and induced fields from QM and PQEq along various directions. We find that the original χ and J parameters (electronegativity and hardness) related to the ionization of the atom remain valid; however, we find that the atomic radius parameter needs to be close to the experimental ionic radii of the transition metals. This leads to a much higher spring constant to describe the atomic polarizability. We find that these optimized parameters for PQEq provide accurate interaction energies compared to QM with charge distributions that depend in a reasonable way on the coordination number and oxidation states of the transition metals. We expect that this description of the electrostatic interactions for TM will be useful in molecular dynamics simulations of inorganic and organometallic materials.

Additional Information

© 2018 American Chemical Society. Received: July 28, 2018; Revised: November 8, 2018; Published: November 9, 2018. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2017R1E1A1A03071049). This work was supported as part of the Computational Materials Sciences Program funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award Number DE-SC00014607. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant ACI-1548562. The authors declare no competing financial interest.

Attached Files

Supplemental Material - jp8b07290_si_001.pdf

Supplemental Material - jp8b07290_si_002.txt

Supplemental Material - jp8b07290_si_003.zip

Files

jp8b07290_si_002.txt
Files (7.7 MB)
Name Size Download all
md5:c759bebd7040c0e8337e72fa146d7f3c
8.1 kB Preview Download
md5:296a861a9d997dde77e51b98a387c2cc
9.7 kB Preview Download
md5:1b1c6dd4e2d851a713902757617cc73e
7.7 MB Preview Download

Additional details

Created:
August 19, 2023
Modified:
October 19, 2023