Next Article in Journal
Metabolomics Research Reveals the Mechanism of Action of Astragalus Polysaccharide in Rats with Digestive System Disorders
Next Article in Special Issue
Structural Changes of the Trinuclear Copper Center in Bilirubin Oxidase upon Reduction
Previous Article in Journal
Deuterated Arachidonic Acids Library for Regulation of Inflammation and Controlled Synthesis of Eicosanoids: An In Vitro Study
Article Menu
Issue 12 (December) cover image

Export Article

Open AccessFeature PaperArticle
Molecules 2018, 23(12), 3332; https://doi.org/10.3390/molecules23123332

Quantitative Assessment of rPM6 for Fluorine- and Chlorine-Containing Metal Complexes: Comparison with Experimental, First-Principles, and Other Semiempirical Results

Graduate School of Information Sciences, Hiroshima City University, 3-4-1 Ozuka-Higashi, Asa-Minami-Ku, Hiroshima 731-3194, Japan
*
Author to whom correspondence should be addressed.
Academic Editors: Yasutaka Kitagawa, Ryohei Kishi and Masayoshi Nakano
Received: 30 November 2018 / Revised: 12 December 2018 / Accepted: 14 December 2018 / Published: 15 December 2018
(This article belongs to the Special Issue Open-Shell Systems for Functional Materials)
  |  
PDF [2596 KB, uploaded 15 December 2018]
  |  

Abstract

We report a reparameterization of PM6 parameters for fluorine and chlorine using our training set containing transition metal complexes. Spin unrestricted calculations with the resulting rPM6 (UrPM6) were examined quantitatively using two test sets: (i) the description of magnetic interactions in 25 dinuclear metal complexes and (ii) the prediction of barrier heights and reaction energies for epoxidation and fluorination reactions catalyzed by high-valent manganese-oxo species. The conventional UPM6 and UPM7 methods were also evaluated for comparison on the basis of either experimental or computational (the UB3LYP/SVP level) outcomes. The merits of UrPM6 are highlighted by both the test sets. As regards magnetic exchange coupling constants, the UrPM6 method had the smallest mean absolute errors from the experimental data (19 cm−1), followed by UPM7 (119 cm−1) and UPM6 (373 cm−1). For the epoxidation and fluorination reactions, all of the transition state searches were successful using UrPM6, while the success rates obtained by UPM6 and UPM7 were only 50%. The UrPM6-optimized stationary points also agreed well with the reference UB3LYP-optimized geometries. The accuracy for estimating reaction energies was also greatly remedied. View Full-Text
Keywords: semiempirical method; magnetic exchange coupling; oxidation reaction semiempirical method; magnetic exchange coupling; oxidation reaction
Figures

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

Supplementary material

SciFeed

Share & Cite This Article

MDPI and ACS Style

Saito, T.; Fujiwara, M.; Takano, Y. Quantitative Assessment of rPM6 for Fluorine- and Chlorine-Containing Metal Complexes: Comparison with Experimental, First-Principles, and Other Semiempirical Results. Molecules 2018, 23, 3332.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top