A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound

A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound

We estimated the redox potential of a model heme compound by using the combination of our density functionals with a computational scheme, which corrects the solvation energy to the normal solvent model. Among many density functionals, the LC-BOP12 functional gave the smallest mean absolute error of...

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Main Authors: Toru Matsui, Jong-Won Song
Format: Article
Language:English
Published: MDPI AG 2019-02-01
Series:Molecules
Subjects:
metal complex
range-separated density functional theory (DFT)
redox potential
Online Access:https://www.mdpi.com/1420-3049/24/4/819
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spelling doaj-72ff5146e6124c78a58aa7f1f61f6c0c2020-11-25T01:13:40ZengMDPI AGMolecules1420-30492019-02-0124481910.3390/molecules24040819molecules24040819A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme CompoundToru Matsui0Jong-Won Song1Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577, JapanDepartment of Chemistry Education, Daegu University, Gyeongsan-si 113-8656, KoreaWe estimated the redox potential of a model heme compound by using the combination of our density functionals with a computational scheme, which corrects the solvation energy to the normal solvent model. Among many density functionals, the LC-BOP12 functional gave the smallest mean absolute error of 0.16 V in the test molecular sets. The application of these methods revealed that the redox potential of a model heme can be controlled within 200 mV by changing the protonation state and even within 20 mV by the flipping of the ligand histidine. In addition, the redox potential depends on the inverse of the dielectric constant, which controls the surroundings. The computational results also imply that a system with a low dielectric constant avoids the charged molecule by controlling either the redox potential or the protonation system.https://www.mdpi.com/1420-3049/24/4/819metal complexrange-separated density functional theory (DFT)redox potential
collection DOAJ
language English
format Article
sources DOAJ
author Toru Matsui
Jong-Won Song
spellingShingle Toru Matsui
Jong-Won Song
A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound
Molecules
metal complex
range-separated density functional theory (DFT)
redox potential
author_facet Toru Matsui
Jong-Won Song
author_sort Toru Matsui
title A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound
title_short A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound
title_full A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound
title_fullStr A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound
title_full_unstemmed A Density Functional Theory-Based Scheme to Compute the Redox Potential of a Transition Metal Complex: Applications to Heme Compound
title_sort density functional theory-based scheme to compute the redox potential of a transition metal complex: applications to heme compound
publisher MDPI AG
series Molecules
issn 1420-3049
publishDate 2019-02-01
description We estimated the redox potential of a model heme compound by using the combination of our density functionals with a computational scheme, which corrects the solvation energy to the normal solvent model. Among many density functionals, the LC-BOP12 functional gave the smallest mean absolute error of 0.16 V in the test molecular sets. The application of these methods revealed that the redox potential of a model heme can be controlled within 200 mV by changing the protonation state and even within 20 mV by the flipping of the ligand histidine. In addition, the redox potential depends on the inverse of the dielectric constant, which controls the surroundings. The computational results also imply that a system with a low dielectric constant avoids the charged molecule by controlling either the redox potential or the protonation system.
topic metal complex
range-separated density functional theory (DFT)
redox potential
url https://www.mdpi.com/1420-3049/24/4/819
work_keys_str_mv AT torumatsui adensityfunctionaltheorybasedschemetocomputetheredoxpotentialofatransitionmetalcomplexapplicationstohemecompound
AT jongwonsong adensityfunctionaltheorybasedschemetocomputetheredoxpotentialofatransitionmetalcomplexapplicationstohemecompound
AT torumatsui densityfunctionaltheorybasedschemetocomputetheredoxpotentialofatransitionmetalcomplexapplicationstohemecompound
AT jongwonsong densityfunctionaltheorybasedschemetocomputetheredoxpotentialofatransitionmetalcomplexapplicationstohemecompound
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