The EEM approach to chemical hardness in molecules and solids: Fundamentals and applications

2006 ◽  
pp. 187-227 ◽  
Author(s):  
Bart G. Baekelandt ◽  
Wilfried J. Mortier ◽  
Robert A. Schoonheydt
Keyword(s):  
Chemical Hardness

On the reliability of volume-based thermodynamics for inorganic-organic salts and coordination compounds with uncharged ligands

2017 ◽  
Author(s):  
Robson de Farias
Keyword(s):  
Coordination Compound ◽  
Coordination Compounds ◽  
Formation Enthalpy ◽  
Lattice Energy ◽  
Chemical Hardness ◽  
Acid Anion ◽  
Organic Salts ◽  
Density Values ◽  
Lattice Energies

In the present work, the reliability of the volume-based thermodynamics (VBT) methods in the calculation of lattice energies is investigated by applying the “traditional” Kapustinskii equation [8], as well as Glasser-Jenkins [3] and Kaya [5] equations to calculate the lattice energies for Na, K and Rb pyruvates [9-11] as well as for the coordination compound [Bi(C<sub>7</sub>H<sub>5</sub>O<sub>3</sub>)<sub>3</sub>C<sub>12</sub>H<sub>8</sub>N<sub>2</sub>] [17] (in which C<sub>12</sub>H<sub>8</sub>N<sub>2</sub> = 1,10 phenathroline and C<sub>7</sub>H<sub>5</sub>O<sub>3</sub><sup>-</sup>= <i>o</i>-hyddroxybenzoic acid anion). As comparison, the lattice energies are also calculated using formation enthalpy values for sodium pyrivate and [Bi(C<sub>7</sub>H<sub>5</sub>O<sub>3</sub>)<sub>3</sub>C<sub>12</sub>H<sub>8</sub>N<sub>2</sub>]. For the pyruvates, is verified that none of the considered approach, Kapustinskii, Glasser, Kaya or density, provides values that agrees in an acceptable % difference, with the lattice energy values calculated from the formation enthalpy values. However, it must be pointed out that Kaya approach, with deals with a chemical hardness approach is the better one for such kind of inorganic-organic salts. Based on data obtained for [Bi(C<sub>7</sub>H<sub>5</sub>O<sub>3</sub>)<sub>3</sub>C<sub>12</sub>H<sub>8</sub>N<sub>2</sub>] is concluded that the only one VBT method that provides reliable lattice energies for compounds with bulky uncharged ligands is that one based on density values (derived by Glasser-Jenkins).

Effect of the intramolecular hydrogen bond in the active metabolite analogs of leflunomide for blocking the Plasmodium falciparum dihydroorotate dehydrogenase enzyme: QTAIM, NBO, and docking study

2020 ◽  
Vol 16 ◽  
Author(s):  
Reihaneh Heidarian ◽  
Mansoureh Zahedi-Tabrizi
Keyword(s):  
Hydrogen Bond ◽  
Plasmodium Falciparum ◽  
Molecular Orbital ◽  
Intramolecular Hydrogen Bond ◽  
Active Metabolite ◽  
Chemical Hardness ◽  
Dihydroorotate Dehydrogenase ◽  
Molecular Orbital Analysis ◽  
Intramolecular Hydrogen ◽  
Orbital Analysis

: Leflunomide (LFM) and its active metabolite, teriflunomide (TFM), have drawn a lot of attention for their anticancer activities, treatment of rheumatoid arthritis and malaria due to their capability to inhibit dihydroorotate dehydrogenase (DHODH) and Plasmodium falciparum dihydroorotate dehydrogenase (PfDHODH) enzyme. In this investigation, the strength of intramolecular hydrogen bond (IHB) in five analogs of TFM (ATFM) has been analyzed employing density functional theory (DFT) using B3LYP/6-311++G (d, p) level and molecular orbital analysis in the gas phase and water solution. A detailed electronic structure study has been performed using the quantum theory of atoms in molecules (QTAIM) and the hydrogen bond energies (EHB) of stable conformer obtained in the range of 76-97 kJ/mol, as a medium hydrogen bond. The effect of substitution on the IHB nature has been studied by natural bond orbital analysis (NBO). 1H NMR calculations show an upward trend in the proton chemical shift of the enolic proton in the chelated ring (14.5 to 15.7ppm) by increasing the IHB strength. All the calculations confirmed the strongest IHB in 5-F-ATFM and the weakest IHB in 2-F-ATFM. Molecular orbital analysis, including the HOMO-LUMO gap and chemical hardness, was performed to compare the reactivity of inhibitors. Finally, molecular docking analysis was carried out to identify the potency of inhibition of these compounds against PfDHODH enzyme.

scholarly journals DFT investigations on arylsulphonyl pyrazole derivatives as potential ligands of selected kinases

2020 ◽  
Vol 18 (1) ◽  
pp. 857-873
Author(s):  
Kornelia Czaja ◽  
Jacek Kujawski ◽  
Radosław Kujawski ◽  
Marek K. Bernard
Keyword(s):  
Free Energy ◽  
Molecular Orbital ◽  
Density Functional ◽  
Chemical Reactivity ◽  
Chemical Hardness ◽  
Free Energy Of Solvation ◽  
Fukui Functions ◽  
Reactivity Descriptors ◽  
Condensed Fukui Functions ◽  
Charge Partitioning

AbstractUsing the density functional theory (DFT) formalism, we have investigated the properties of some arylsulphonyl indazole derivatives that we studied previously for their biological activity and susceptibility to interactions of azoles. This study includes the following physicochemical properties of these derivatives: electronegativity and polarisability (Mulliken charges, adjusted charge partitioning, and iterative-adjusted charge partitioning approaches); free energy of solvation (solvation model based on density model and M062X functional); highest occupied molecular orbital (HOMO)–lowest occupied molecular orbital (LUMO) gap together with the corresponding condensed Fukui functions, time-dependent DFT along with the UV spectra simulations using B3LYP, CAM-B3LYP, MPW1PW91, and WB97XD functionals, as well as linear response polarisable continuum model; and estimation of global chemical reactivity descriptors, particularly the chemical hardness factor. The charges on pyrrolic and pyridinic nitrogen (the latter one in the quinolone ring of compound 8, as well as condensed Fukui functions) reveal a significant role of these atoms in potential interactions of azole ligand–protein binding pocket. The lowest negative value of free energy of solvation can be attributed to carbazole 6, whereas pyrazole 7 has the least negative value of this energy. Moreover, the HOMO–LUMO gap and chemical hardness show that carbazole 6 and indole 5 exist as soft molecules, while fused pyrazole 7 has hard character.

Reactivity Indices for ortho/para Monosubstituted Phenols

2007 ◽  
Vol 10 (1) ◽  
Author(s):  
Nevim San ◽  
Murat Kılıç ◽  
Zekiye Çınar
Keyword(s):  
Photocatalytic Degradation ◽  
Density Functional ◽  
Reaction Rates ◽  
Chemical Hardness ◽  
Fukui Functions ◽  
Reactivity Descriptors ◽  
Degradation Reactions ◽  
The Density Functional Theory ◽  
Local Softness ◽  
Soft Interactions

AbstractThe kinetics of the photocatalytic degradation reactions of twelve ortho/para mono-substituted phenols containing electron-donating or -withdrawing groups have been investigated experimentally. With the intention of determining the most suitable DFT reactivity descriptors, geometry optimizations of the compounds have been performed with the Density Functional Theory DFT at B3LYP/6-31G* level. In order to take the effect of solvent water into account, the calculations have been repeated for the optimized structures by using COSMO as the solvation model. Chemical hardness, softness, electronegativities, Fukui functions, local hardness and softness, local electrophilicities and softness differences for all phenol molecules have been calculated. Correlations between the apparent initial first-order rate constants determined in the experiments and the calculated DFT reactivity descriptors have been examined. Results show that the reactions investigated are electrophilic in nature. The local softness and softness differences correlate well with the reaction rates indicating that soft-soft interactions dominate in the photocatalytic degradation reactions of phenols.

scholarly journals Theoretical Study of Solvent Effects on the Electronic and Thermodynamic Properties of Tetrathiafulvalene (TTF) Molecule Based on DFT

2021 ◽  
pp. 42-54
Author(s):  
Rabiu Nuhu Muhammad ◽  
N. M. Mahraz ◽  
A. S Gidado ◽  
A. Musa
Keyword(s):  
Thermodynamic Properties ◽  
Bond Length ◽  
Density Functional ◽  
Theoretical Study ◽  
Energy Gap ◽  
Basis Set ◽  
Basis Sets ◽  
Frontier Molecular Orbital ◽  
Orbital Energy ◽  
Chemical Hardness

Tetrathiafulvalene () is an organosulfur compound used in the production of molecular devices such as switches, sensors, nonlinear optical devices and rectifiers. In this work, a theoretical study on the effects of solvent on TTF molecule was investigated and reported based on Density Functional Theory (DFT) as implemented in Gaussian 03 package using B3LYP/6-31++G(d,p) basis set. Different solvents were introduced as a bridge to investigate their effects on the electronic structure. The HUMO, LUMO, energy gap, global chemical index, thermodynamic properties, NLO and DOS analysis of the TTF molecule in order to determine the reactivity and stability of the molecule were obtained. The results obtained showed that the solvents have effects on the electronic and non-linear-optical properties of the molecule. The optimized bond length revealed that the molecule has strong bond in gas phase with smallest bond length of about 1.0834Å than in the rest of the solvents. It was observed that the molecule is more stable in acetonitrile with HOMO-LUMO gap and chemical hardness of 3.6373eV and 1.8187eV respectively. This indicates that the energy gap and chemical hardness of TTF molecule increases with the increase in polarity and dielectric constant of the solvents. The computed results agreed with the results in the literature. The thermodynamics and NLO properties calculation also indicated that TTF molecule has highest value of specific heat capacity (Cv), total dipole moment () and first order hyperpolarizability () in acetonitrile, while acetone has the highest value of entropy and toluene has a slightly higher value of zero point vibrational energy (ZPVE) than the rest of the solvents. The results show that careful selection of the solvents and basis sets can tune the frontier molecular orbital energy gap of the molecule and can be used for molecular device applications.

scholarly journals Detemination of The Best Method (HF, MP2 and B3LYP) in Calculation of Chemical Hardness

2018 ◽  
Vol 2 (2) ◽  
pp. 7-15 ◽  
Author(s):  
Zinet Zaim ◽  
Tuba Alagöz Sayın ◽  
Koray Sayın ◽  
Duran Karakaş
Keyword(s):  
Chemical Hardness

Synthesis and DFT Studies of Pyrimidin-1(2H)-ylaminofumarate Derivatives

2020 ◽  
Vol 42 (5) ◽  
pp. 746-746
Author(s):  
Murat Saracoglu Murat Saracoglu ◽  
Zulbiye Kokbudak Zulbiye Kokbudak ◽  
M Izzettin Yilmazer and Fatma Kandemirli M Izzettin Yilmazer and Fatma Kandemirli
Keyword(s):  
Quantum Chemical ◽  
Energy Gap ◽  
Basis Set ◽  
Chemical Hardness ◽  
Pyrimidine Derivatives ◽  
1H And 13C Nmr ◽  
Solvent Phase ◽  
B3lyp Method ◽  
Ft Ir ◽  
New Compounds

Pyrimidine derivatives have biological and pharmacological properties. Therefore, in this study we focused on the synthesis various Pyrimidine derivatives to make noteworthy contributions this class of heterocyclic compounds. In the present study, the new compounds (4-6) were obtained by the reactions of 1-amino-5-benzoyl-4-phenylpyrimidin-2(1H)-one (1), 1-amino-5-(4-methylbenzoyl)-4-(4-methylphenyl)pyrimidin-2(1H)-one (2) and 1-amino-5-(4-methoxybenzoyl)-4-(4-methoxyphenyl)pyrimidin-2(1H)-one (3) with dimethyl acetylenedicarboxylate. The structures of these compounds were proved by elemental analysis, FT-IR, 1H and 13C-NMR spectra. In addition to, quantum chemical calculations were made to find molecular properties of the pyrimidin-1(2H)-ylaminofumarate derivatives (4-6) by using DFT/B3LYP method with 6-311++G(2d,2p) basis set. Quantum chemical features such as EHOMO, ELUMO, energy gap, ionization potential, chemical hardness, chemical softness, electronegativity etc. values for gas and solvent phase of neutral molecules were calculated and discussed.

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