Reliable Quantum Chemical Prediction of the Localized/Delocalized Character of Organic Mixed-Valence Radical Anions. From Continuum Solvent Models to Direct-COSMO-RS

AbstractThe validation of octanol-water partition coefficients (logP) quantum chemical calculations is presented for 27 alkane alcohols. The chemical accuracy of predicted logPvalues was estimated for six DFT functionals (B3LYP, PBE0, M06-2X, ωB97X-D, B97-D3, M11) and three implicit solvent models. Triple-zeta basis set 6-311++G(d,p) was employed. The best linear correlation with the experimental logPvalues was achieved for the B3LYP and B97-D3 functionals combined with the SMD model. On the other hand, no linearity was found when IEF-PCM or C-PCM implicit models were employed.

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Examining the Assumptions Underlying Continuum-Solvent Models

Journal of Chemical Theory and Computation ◽

10.1021/acs.jctc.5b00684 ◽

2015 ◽

Vol 11 (10) ◽

pp. 4593-4600 ◽

Cited By ~ 15

Author(s):

Robert C. Harris ◽

B. Montgomery Pettitt

Keyword(s):

Solvent Models ◽

Continuum Solvent Models

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Boundary continuity and analytical potentials in continuum solvent models. Implications for the Born model

The Journal of Physical Chemistry ◽

10.1021/j100291a036 ◽

1987 ◽

Vol 91 (7) ◽

pp. 1868-1873 ◽

Cited By ~ 18

Author(s):

S. Ehrenson

Keyword(s):

Born Model ◽

Solvent Models ◽

Continuum Solvent Models

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Quantum-chemical insights into mixed-valence systems: within and beyond the Robin–Day scheme

Chemical Society Reviews ◽

10.1039/c3cs60481k ◽

2014 ◽

Vol 43 (14) ◽

pp. 5067-5088 ◽

Cited By ~ 108

Author(s):

M. Parthey ◽

M. Kaupp

Keyword(s):

Transition Metal ◽

Quantum Chemical ◽

Mixed Valence ◽

Chemical Methods ◽

Quantum Chemical Methods

The application of quantum-chemical methods to both organic and transition-metal mixed-valence systems is reviewed, with particular emphasis on how to describe correctly delocalisation vs. localisation near the borderline between Robin–Day classes II and III.

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A Reliable Quantum-Chemical Protocol for the Characterization of Organic Mixed-Valence Compounds

Journal of the American Chemical Society ◽

10.1021/ja9070859 ◽

2009 ◽

Vol 131 (44) ◽

pp. 16292-16302 ◽

Cited By ~ 140

Author(s):

Manuel Renz ◽

Kolja Theilacker ◽

Christoph Lambert ◽

Martin Kaupp

Keyword(s):

Quantum Chemical ◽

Mixed Valence ◽

Mixed Valence Compounds

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Ferromagnetic Coupling in a Mixed-Valence Hexavanadate Core: Quantum-Chemical Forecast

European Journal of Inorganic Chemistry ◽

10.1002/ejic.200700421 ◽

2007 ◽

Vol 2007 (27) ◽

pp. 4317-4325 ◽

Cited By ~ 23

Author(s):

Ekaterina M. Zueva ◽

Serguei A. Borshch ◽

Maria M. Petrova ◽

Henry Chermette ◽

Andrey M. Kuznetsov

Keyword(s):

Quantum Chemical ◽

Mixed Valence ◽

Ferromagnetic Coupling

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Evaluation of Docking Target Functions by the Comprehensive Investigation of Protein-Ligand Energy Minima

Advances in Bioinformatics ◽

10.1155/2015/126858 ◽

2015 ◽

Vol 2015 ◽

pp. 1-12 ◽

Cited By ~ 23

Author(s):

Igor V. Oferkin ◽

Ekaterina V. Katkova ◽

Alexey V. Sulimov ◽

Danil C. Kutov ◽

Sergey I. Sobolev ◽

...

Keyword(s):

Ligand Binding ◽

Force Field ◽

Quantum Chemical ◽

Target Function ◽

Binding Energies ◽

Low Energy ◽

Implicit Solvent ◽

Energy Calculation ◽

Solvent Models ◽

Docking Program

The adequate choice of the docking target function impacts the accuracy of the ligand positioning as well as the accuracy of the protein-ligand binding energy calculation. To evaluate a docking target function we compared positions of its minima with the experimentally known pose of the ligand in the protein active site. We evaluated five docking target functions based on either the MMFF94 force field or the PM7 quantum-chemical method with or without implicit solvent models: PCM, COSMO, and SGB. Each function was tested on the same set of 16 protein-ligand complexes. For exhaustive low-energy minima search the novel MPI parallelized docking program FLM and large supercomputer resources were used. Protein-ligand binding energies calculated using low-energy minima were compared with experimental values. It was demonstrated that the docking target function on the base of the MMFF94 force field in vacuo can be used for discovery of native or near native ligand positions by finding the low-energy local minima spectrum of the target function. The importance of solute-solvent interaction for the correct ligand positioning is demonstrated. It is shown that docking accuracy can be improved by replacement of the MMFF94 force field by the new semiempirical quantum-chemical PM7 method.

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