Revisiting the calculation of condensed Fukui functions using the quantum theory of atoms in molecules

2007 ◽  
Vol 126 (23) ◽  
pp. 234108 ◽  
Author(s):  
Nicolás Otero ◽  
Marcos Mandado ◽  
Ricardo A. Mosquera
Keyword(s):  
Quantum Theory ◽  
Atoms In Molecules ◽  
Fukui Functions ◽  
Condensed Fukui Functions

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.

Machine Learning Estimation of Atom Condensed Fukui Functions

2015 ◽  
Vol 35 (2) ◽  
pp. 62-69 ◽  
Author(s):  
Qingyou Zhang ◽  
Fangfang Zheng ◽  
Tanfeng Zhao ◽  
Xiaohui Qu ◽  
João Aires-de-Sousa
Keyword(s):  
Machine Learning ◽  
Fukui Functions ◽  
Condensed Fukui Functions

Ab initio charge density analysis of (B6C)2– and B4C3 species — How to describe the bonding pattern?

2006 ◽  
Vol 84 (5) ◽  
pp. 771-781 ◽  
Author(s):  
Cina Foroutan-Nejad ◽  
Gholam Hossein Shafiee ◽  
Abdolreza Sadjadi ◽  
Shant Shahbazian
Keyword(s):  
Quantum Theory ◽  
Carbon Atom ◽  
Charge Density ◽  
Ab Initio ◽  
Atoms In Molecules ◽  
Central Carbon Atom ◽  
B3lyp Method ◽  
Central Carbon ◽  
Density Analysis ◽  
Concrete Ring

In this study, a detailed topological charge density analysis based on the quantum theory of atoms in molecules (QTAIM) developed by Bader and co-workers, has been accomplished (using the B3LYP method) on the CB62– anion and three planar isomers of the C3B4 species, which had been first proposed by Exner and Schleyer as examples of molecules containing hexacoordinate carbon atoms. The analysis uncovers the strong (covalent) interactions of boron atoms as well as the "nondirectional" interaction of central carbon atom with those peripheral atoms. On the other hand, instabilities have been found in the topological networks of (B6C)2– and B4C3(para) species. A detailed investigation of these instabilities demonstrates that the topology of charge density has a floppy nature near the equilibrium geometries of the species under study. Thus, these species seems to be best described as complexes of a relatively concrete ring containing boron or carbon atoms and a central carbon atom that is confined in the plane of the molecule, but with nondirectional interactions with the surrounding atoms.Key words: hypervalency, hexacoordinate carbon, quantum theory of atoms in molecules, charge density analysis, ab initio methods.

scholarly journals Decomposition of d- and f-Shell Contributions to Uranium Bonding from the Quantum Theory of Atoms in Molecules: Application to Uranium and Uranyl Halides

Inorganics ◽  
2018 ◽  
Vol 6 (3) ◽  
pp. 88 ◽  
Author(s):  
Jonathan Tanti ◽  
Meghan Lincoln ◽  
Andy Kerridge
Keyword(s):  
Quantum Theory ◽  
Electronic Structures ◽  
Density Functional ◽  
Covalent Bond ◽  
Vibrational Frequencies ◽  
Atoms In Molecules ◽  
High Symmetry ◽  
Strong Correlations ◽  
Bond Stability ◽  
Fluoride Ligands

The electronic structures of a series of uranium hexahalide and uranyl tetrahalide complexes were simulated at the density functional theoretical (DFT) level. The resulting electronic structures were analyzed using a novel application of the Quantum Theory of Atoms in Molecules (QTAIM) by exploiting the high symmetry of the complexes to determine 5f- and 6d-shell contributions to bonding via symmetry arguments. This analysis revealed fluoride ligation to result in strong bonds with a significant covalent character while ligation by chloride and bromide species resulted in more ionic interactions with little differentiation between the ligands. Fluoride ligands were also found to be most capable of perturbing an existing electronic structure. 5f contributions to overlap-driven covalency were found to be larger than 6d contributions for all interactions in all complexes studied while degeneracy-driven covalent contributions showed significantly greater variation. σ-contributions to degeneracy-driven covalency were found to be consistently larger than those of individual π-components while the total π-contribution was, in some cases, larger. Strong correlations were found between overlap-driven covalent bond contributions, U–O vibrational frequencies, and energetic stability, which indicates that overlap-driven covalency leads to bond stabilization in these complexes and that uranyl vibrational frequencies can be used to quantitatively probe equatorial bond covalency. For uranium hexahalides, degeneracy-driven covalency was found to anti-correlate with bond stability.

On the transferability of electron density in binary vanadium borides VB, V3B4 and VB2

2015 ◽  
Vol 71 (6) ◽  
pp. 777-787 ◽  
Author(s):  
Bürgehan Terlan ◽  
Lev Akselrud ◽  
Alexey I. Baranov ◽  
Horst Borrmann ◽  
Yuri Grin
Keyword(s):  
Quantum Theory ◽  
Crystal Structures ◽  
Electron Density ◽  
Critical Points ◽  
Atoms In Molecules ◽  
Model Systems ◽  
Suitable Model ◽  
Interatomic Distances ◽  
Systematic Analysis ◽  
A Charge

Binary vanadium borides are suitable model systems for a systematic analysis of the transferability concept in intermetallic compounds due to chemical intergrowth in their crystal structures. In order to underline this structural relationship, topological properties of the electron density in VB, V3B4 and VB2 reconstructed from high-resolution single-crystal X-ray diffraction data as well as derived from quantum chemical calculations, are analysed in terms of Bader's Quantum Theory of Atoms in Molecules [Bader (1990). Atoms in Molecules: A Quantum Theory, 1st ed. Oxford: Clarendon Press]. The compounds VB, V3B4 and VB2 are characterized by a charge transfer from the metal to boron together with two predominant atomic interactions, the shared covalent B—B interactions and the polar covalent B—M interactions. The resembling features of the crystal structures are well reflected by the respective B—B interatomic distances as well as by ρ(r) values at the B—B bond critical points. The latter decrease with an increase in the corresponding interatomic distances. The B—B bonds show transferable electron density properties at bond critical points depending on the respective bond distances.

scholarly journals ELECTRONIC STRUCTURE OF METHYLIDINESULFOXIDALCANES

2020 ◽  
pp. 106-113
Author(s):  
Наталья Петровна Русакова ◽  
Елена Михайловна Чернова ◽  
Владимир Владимирович Туровцев ◽  
Юрий Димитриевич Орлов
Keyword(s):  
Electronic Structure ◽  
Quantum Theory ◽  
Functional Groups ◽  
Atoms In Molecules

В рамках «квантовой теории атомов в молекулах» (QTAIM) определено электронное строение молекул ряда метилидинсульфоксидалканов n-C H-S(О)СН, где 1 ≤ n ≤ 10. Составлена качественная шкала электроотрицательностей функциональных групп. Within the framework of the «quantum theory of atoms in molecules» (QTAIM), the electronic structure of the molecules of a series of methylidinesulfoxidealkanes n-CH-S(О)СН, where 1 ≤ n ≤ 10, was determined. A qualitative scale of electronegativities of functional groups was compiled.

scholarly journals π-Hole Tetrel Bonds—Lewis Acid Properties of Metallylenes

Crystals ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 112
Author(s):  
Sławomir J. Grabowski
Keyword(s):  
Quantum Theory ◽  
Crystal Structures ◽  
Lewis Acid ◽  
Natural Bond Orbital ◽  
Database Search ◽  
Lewis Base ◽  
Atoms In Molecules ◽  
Acid Properties ◽  
Structural Database ◽  
Tetrel Bonds

The MP2/aug-cc-pVTZ calculations were performed on the dihalometallylenes to indicate their Lewis acid and Lewis base sites. The results of the Cambridge Structural Database search show corresponding and related crystal structures where the tetrel center often possesses the configuration of a trigonal bipyramid or octahedron. The calculations were also carried out on dimers of dichlorogermylene and dibromogermylene and on complexes of these germylenes with one and two 1,4-dioxide molecules. The Ge⋯Cl, Ge⋯Br, and Ge⋯O interactions are analyzed. The Ge⋯O interactions in the above mentioned germylene complexes may be classified as the π-hole tetrel bonds. The MP2 calculations are supported by the results of the Quantum Theory of Atoms in Molecules (QTAIM) and the Natural Bond Orbital (NBO) approaches.

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