Local chemical potential, local hardness, and dual descriptors in temperature dependent chemical reactivity theory

2017 ◽  
Vol 19 (21) ◽  
pp. 13687-13695 ◽  
Author(s):  
Marco Franco-Pérez ◽  
Paul W. Ayers ◽  
José L. Gázquez ◽  
Alberto Vela
Keyword(s):  
Chemical Potential ◽  
Chemical Reactivity ◽  
Potential Well ◽  
Temperature Dependent ◽  
Local Hardness ◽  
Chemical Reactivity Theory ◽  
Definition Of

From the definition of a local chemical potential, well-behaved expressions for the local hardness and the dual descriptors are derived.

New Fukui, dual and hyper-dual kernels as bond reactivity descriptors

2017 ◽  
Vol 19 (24) ◽  
pp. 16095-16104 ◽  
Author(s):  
Marco Franco-Pérez ◽  
Carlos-A Polanco-Ramírez ◽  
Paul W. Ayers ◽  
José L. Gázquez ◽  
Alberto Vela
Keyword(s):  
Chemical Reactivity ◽  
Temperature Dependent ◽  
Reactivity Descriptors ◽  
Chemical Reactivity Theory

Three new bond reactivity indicators are presented within the framework of the temperature dependent chemical reactivity theory.

scholarly journals Anticancer Indole-Based Chalcones: A Structural and Theoretical Analysis

Molecules ◽  
2019 ◽  
Vol 24 (20) ◽  
pp. 3728 ◽  
Author(s):  
Farid A. Badria ◽  
Saied M. Soliman ◽  
Saleh Atef ◽  
Mohammad Shahidul Islam ◽  
Abdullah Mohammed Al-Majid ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Theoretical Analysis ◽  
Dft Calculations ◽  
Density Functional ◽  
Chemical Potential ◽  
Chemical Reactivity ◽  
Stacking Interactions ◽  
Functional Theory ◽  
Topology Analysis ◽  
Reactivity Indices

The crystal structures of five new chalcones derived from N-ethyl-3-acetylindole with different substituents were investigated: (E)-3-(4-bromophenyl)-1-(1-ethyl-1H-indol-3-yl)prop-2-en-1-one (3a); (E)-3-(3-bromophenyl)-1-(1-ethyl-1H-indol-3-yl)prop-2-en-1-one (3b); (E)-1-(1-ethyl-1H-indol-3-yl)-3-(4-methoxyphenyl)prop-2-en-1-one (3c); (E)-1-(1-ethyl-1H-indol-3-yl)-3-mesitylprop-2-en-1-one (3d); and (E)-1-(1-ethyl-1H-indol-3-yl)-3-(furan-2-yl)prop-2-en-1-one (3e). The molecular packing of the studied compounds is controlled mainly by C–H⋅⋅⋅O hydrogen bonds, C–H⋅⋅⋅π interactions, and π···π stacking interactions, which were quantitatively analyzed using Hirshfeld topology analysis. Using density functional theory (DFT) calculations, the order of polarity (3b ˂ 3d ˂ 3e ˂ 3a ˂ 3c) was determined. Several chemical reactivity indices such as the ionization potential (I), electron affinity (A), chemical potential (μ), hardness (η), electrophilicity (ω) and nucleophilicity (N) indices were calculated, and these properties are discussed and compared. In addition, the antiproliferative activity of the five new chalcones was studied.

Roaming Reactions and Dynamics in the van der Waals Region

2020 ◽  
Vol 71 (1) ◽  
pp. 77-100 ◽  
Author(s):  
Arthur G. Suits
Keyword(s):  
Long Range ◽  
Internal State ◽  
Chemical Reactivity ◽  
Van Der Waals ◽  
Quantum Effects ◽  
Experimental Results ◽  
Unexpected Formation ◽  
Chemical Systems ◽  
Definition Of

Roaming reactions were first clearly identified in photodissociation of formaldehyde 15 years ago, and roaming dynamics are now recognized as a universal aspect of chemical reactivity. These reactions typically involve frustrated near-dissociation of a quasibound system to radical fragments, followed by reorientation at long range and intramolecular abstraction. The consequences can be unexpected formation of molecular products, depletion of the radical pool in chemical systems, and formation of products with unusual internal state distributions. In this review, I examine some current aspects of roaming reactions with an emphasis on experimental results, focusing on possible quantum effects in roaming and roaming dynamics in bimolecular systems. These considerations lead to a more inclusive definition of roaming reactions as those for which key dynamics take place at long range.

scholarly journals Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes

Molecules ◽  
2020 ◽  
Vol 25 (18) ◽  
pp. 4043 ◽  
Author(s):  
Temiloluwa T. Adejumo ◽  
Nikolaos V. Tzouras ◽  
Leandros P. Zorba ◽  
Dušanka Radanović ◽  
Andrej Pevec ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Gas Phase ◽  
Molecular Orbital ◽  
Density Functional ◽  
Chemical Potential ◽  
Chemical Reactivity ◽  
Geometry Optimization ◽  
Coupling Reaction ◽  
Functional Theory ◽  
Reactivity Descriptors

Two new Zn(II) complexes with tridentate hydrazone-based ligands (condensation products of 2-acetylthiazole) were synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction methods. The complexes 1, 2 and recently synthesized [ZnL3(NCS)2] (L3 = (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex 3 were tested as potential catalysts for the ketone-amine-alkyne (KA2) coupling reaction. The gas-phase geometry optimization of newly synthesized and characterized Zn(II) complexes has been computed at the density functional theory (DFT)/B3LYP/6–31G level of theory, while the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) energies were calculated within the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G and B3LYP/6-311G(d,p) levels of theory. From the energies of frontier molecular orbitals (HOMO–LUMO), the reactivity descriptors, such as chemical potential (μ), hardness (η), softness (S), electronegativity (χ) and electrophilicity index (ω) have been calculated. The energetic behavior of the investigated compounds (1 and 2) has been examined in gas phase and solvent media using the polarizable continuum model. For comparison reasons, the same calculations have been performed for recently synthesized [ZnL3(NCS)2] complex 3. DFT results show that compound 1 has the smaller frontier orbital gap so, it is more polarizable and is associated with a higher chemical reactivity, low kinetic stability and is termed as soft molecule.

New molecular target insights about protein kinases of the Plasmodium falciparum. Using molecular docking and DFT-based reactivity descriptors

2017 ◽  
Vol 16 (08) ◽  
pp. 1750076 ◽  
Author(s):  
Alejandro Morales-Bayuelo
Keyword(s):  
Plasmodium Falciparum ◽  
Protein Kinases ◽  
Density Functional ◽  
Chemical Potential ◽  
Chemical Reactivity ◽  
Binding Pocket ◽  
Fukui Functions ◽  
Reactivity Descriptors ◽  
Chemical Reactivity Descriptors ◽  
Hinge Zone

Currently, there is increasing interest in the potential of malaria inhibitors in Plasmodium falciparum activity. In this work, is propose a possible alternative to classifying 154 antimalarials, with P. falciparum activity. These antimalarials were synthesized by the Chibale’s group ( http://www.kellychibaleresearch.uct.ac.za/ ), with the goal of finding new insights on the binding pocket of the protein kinase PfPK5, PfPK7, PfCDPK1, PfCDPK4, PfMAP1, and PfPK6 of the malaria parasite. However, there is only information about crystallography of PfPK5 and PfPK7. The protein kinases PfCDPK1, PfCDPK4, PfMAP1, and PfPK6 were modeled using molecular homology. The validation used shows that our homology models can be an alternative for the protein kinases from P. falciparum, unknown today. The antimalarials were classified by taking into account the interactions in the hinge zone. These ligands bind to the kinase through the formation of one of two hydrogen bonds, with the backbone residues of the hinge region connecting the kinase N- and C-terminal loops. These interactions were supported by a reactivity chemistry analysis, using global chemical reactivity descriptors such as chemical potential, hardness, softness, electrophilicity, and the Fukui functions as local reactivity descriptors, within the Density Functional Theory (DFT) context.

Rutile Molecular Model and its EUC Determination by PM7

2014 ◽  
Vol 976 ◽  
pp. 260-264
Author(s):  
C.H. Rios-Reyes ◽  
Luis Humberto Mendoza Huizar ◽  
Juan Coreño-Alonso
Keyword(s):  
Band Gap ◽  
Electronic Properties ◽  
Chemical Potential ◽  
Molecular Model ◽  
Theoretical Calculations ◽  
Chemical Reactivity ◽  
Total Hardness ◽  
Physical Parameters ◽  
Reactivity Descriptors ◽  
Cluster Properties

Rutile surface has been modeled in order to study its electronic properties as well as to determine its surface chemical reactivity. There have been constructed 10 different rutile structures, from a 6 atoms cluster (for the smallest) to a 356 atoms cluster (for the biggest). It was calculated for each cluster some physical parameters which are related to the electronic properties, such as work function, band gap, and density of states (DOS), in order to analyze the tendency of the cluster properties with the increase of atoms. From the data obtained, it was determined the Electronic Unit Cell (EUC), which refers to the modeled structure for what the electronic and reactivity properties of the system does no change, from clusters with different number of atoms. From the rutile EUC cluster it was determined its band gap with a value of 3.28 eV, which agreed with the experimental value of 3.0-3.1 eV. Furthermore, it was performed a reactivity surface study, which comprised the analysis of reactivity descriptors such as ionization potential, electronic affinity, total hardness, electronic chemical potential, electrophilicity and electronegativity. All theoretical calculations were performed using the semiempirical PM7 included in the 2012 version of MOPAC and the surfaces were modeled from crystallographic data.

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