Topological properties of the electronic structures of the reactants, transition states, and products of the reactions of the hydroxyl radical with the series C2HnF6−n, n = 1–6

1996 ◽  
Vol 74 (6) ◽  
pp. 786-800 ◽  
Author(s):  
Jaime M. Martell ◽  
James B. Tee ◽  
Russell J. Boyd
Keyword(s):  
Hydroxyl Radical ◽  
Electron Density ◽  
Critical Points ◽  
Population Analysis ◽  
Transition States ◽  
Reaction Centre ◽  
Topological Properties ◽  
Mulliken Population ◽  
Dissociation Energies ◽  
Reaction Proceeds

Properties of the bond critical points, including the electron density and its Laplacian, and distances to bonded nuclei, for all species (reactants, transition states, and products) in the reactions of the hydroxyl radical with the series C2HnF6−nn = 1–6 were calculated using Bader's atoms-in-molecules methodology. The electron density and its Laplacian at the bond critical points correlate with bond strength, as measured by bond dissociation energies. The positions of the bond critical points vary with the electronegativity of surrounding atoms. Charge development in the course of the reactions was monitored using Mulliken population analysis at the HF/6-31G(d), HF/6-311G(d,p)//HF/6-31G(d), MP2/6-311G(d,p)//HF/6-31G(d), and HF/6-311G(d,p)//MP2/6-31G(d,p) levels of theory, and natural population analysis and Bader population analysis at the highest common level of theory, MP2/6-311G(d,p)//HF/6-31G(d). In general, there is a buildup of charge in the transition states, concentrated near the reaction centre, which dissipates somewhat as the reaction proceeds to products. The description of charge transfer varies somewhat with the three methods. Key words: topological properties, atomic charges, charge development, reactions of the hydroxyl radical with fluorinated ethanes.

scholarly journals Co-ordination ability of Vinyl Imidazole(VIm), Imidazole(Im), Indazole(In), Ammonia(NH3) and Dimethyl sulphoxide (DMSO) Ligands in Ruthenium Complexes

2020 ◽  
Vol 36 (6) ◽  
pp. 1134-1142
Author(s):  
Rahul Sarma Baruah ◽  
Rinki Moni Kalita ◽  
Chitrani Medhi
Keyword(s):  
Electron Density ◽  
Population Analysis ◽  
Donor Site ◽  
Slight Variation ◽  
Dissociation Energies ◽  
Density Mapping ◽  
Anti Cancer ◽  
Coordinate Bond ◽  
Ru Complexes ◽  
Homo Lumo

Few essential electronic properties of potential anti-cancer complexes are examined using quantum mechanical calculations. The co-ordination ability of these ligands with the central Ru metal has been assessed. The ionization energies and HOMO-LUMO gaps are used to explain the coordinate bond formation between ligand and Ru. The variation of charges from natural population analysis(NPA) of the donor sites of ligands is fairly similar to the trends in the coordinate bond distances despite the presence of other ligands in these Ru complexes. Slight variation of coordinate bonds (Ru-donor site) has been found. In addition, Cl dissociation energies from these complexes do not vary much and the trend of the energy values are similar to oxidation energies of these complexes. The NPA charges and HOMO-LUMO electron density mapping indicate that the electron density around Ru metal is increasing, which suggests that the migration of electron density is towards Ru.

scholarly journals Quantum-chemical study of the active sites of camptothecin through their Cu(II) coordination ability

2018 ◽  
Vol 11 (1) ◽  
pp. 6-10
Author(s):  
Marek Štekláč ◽  
Martin Breza
Keyword(s):  
Electron Density ◽  
Active Sites ◽  
Population Analysis ◽  
Topological Analysis ◽  
Quantum Chemical Study ◽  
Chemical Study ◽  
Mulliken Population ◽  
Coordination Ability ◽  
Geometrical Factors ◽  
The One

Abstract The structures of camptothecin (CPT) lactone form and its complexes with Cu(II) were optimized at B3LYP/6-311G* level of theory. Their electronic structures were evaluated via QTAIM topological analysis of electron density and Mulliken population analysis. Stability, electron density distribution and geometrical factors of the optimized systems were compared. Both CPT nitrogen atoms show lower affinity to Cu(II) compared to the oxygen ones. Both the oxygen atom in the CPT lactone ring and the one in the neighbouring carbonyl group show the highest affinity to Cu(II) and the highest stability of Cu-CPT complexes which indicates the most probable CPT reaction sites.

scholarly journals Quantum chemistry study on the promoted reactivity of substituted cyclooctynes in bioorthogonal cycloaddition reactions

2021 ◽  
Vol 27 (1) ◽  
pp. 142-154
Author(s):  
Tayebeh Hosseinnejad ◽  
Marzieh Omrani-Pachin
Keyword(s):  
Activation Energy ◽  
Quantum Theory ◽  
Quantum Chemistry ◽  
Electron Density ◽  
Critical Points ◽  
Cycloaddition Reaction ◽  
Electronic Energy ◽  
The Other ◽  
Dipolar Cycloaddition ◽  
Topological Properties

Abstract In the present research, we focus on the energetics and electronic aspects of enhanced reactivity in the regioselective bioorthogonal 1,3-dipolar cycloaddition reaction of various substituted cyclooctynes with methyl azide, applying quantum chemistry approaches. In this respect, we assessed the structural and energetic properties of regioisomeric products and their corresponded transition states and calculated the reaction electronic energy changes and energy barriers through the cycloaddition pathways. The obtained results revealed that the trifluoromethyl substitution and fluorination of cyclooctynes lead to improved reactivity, in conjunction with increased exothermicity and decreased activation energy values. On the other hand, quantum theory of atoms in molecules computations were performed on some key bond and ring critical points that demonstrated the stabilizing topological properties of electron density and its derivatives upon trifluoromethyl substitution and fluorination of propargylic carbon of cyclooctynes which can be regarded as the essential origin of enhanced reactivity.

scholarly journals Ni Oxidation State and Ligand Saturation Impact on the Capability of Octaazamacrocyclic Complexes to Bind and Reduce CO2

Molecules ◽  
2021 ◽  
Vol 26 (14) ◽  
pp. 4139
Author(s):  
Barbora Vénosová ◽  
Ingrid Jelemenská ◽  
Jozef Kožíšek ◽  
Peter Rapta ◽  
Michal Zalibera ◽  
...  
Keyword(s):  
Quantum Theory ◽  
Oxidation State ◽  
Central Atom ◽  
Population Analysis ◽  
Mulliken Population Analysis ◽  
Mulliken Population ◽  
Theoretical Methods ◽  
Ni Oxidation ◽  
Shed Light

Two 15-membered octaazamacrocyclic nickel(II) complexes are investigated by theoretical methods to shed light on their affinity forwards binding and reducing CO2. In the first complex 1[NiIIL]0, the octaazamacrocyclic ligand is grossly unsaturated (π-conjugated), while in the second 1[NiIILH]2+ one, the macrocycle is saturated with hydrogens. One and two-electron reductions are described using Mulliken population analysis, quantum theory of atoms in molecules, localized orbitals, and domain averaged fermi holes, including the characterization of the Ni-CCO2 bond and the oxidation state of the central Ni atom. It was found that in the [NiLH] complex, the central atom is reduced to Ni0 and/or NiI and is thus able to bind CO2 via a single σ bond. In addition, the two-electron reduced 3[NiL]2− species also shows an affinity forwards CO2.

Electron Pairing and Chemical Bonds. Physical Meaning of Effective Pairs

1994 ◽  
Vol 59 (12) ◽  
pp. 2567-2578 ◽  
Author(s):  
Robert Ponec ◽  
Filip Uhlík
Keyword(s):  
Density Distribution ◽  
Electron Density ◽  
Physical Meaning ◽  
Electron Density Distribution ◽  
Mutual Coupling ◽  
Population Analysis ◽  
Point Of View ◽  
Chemical Bonds ◽  
Conditional Probabilities ◽  
Electron Pairing

The physical meaning of the so-called effective pairs which have been introduced recently within the formalism of pair population analysis is discussed using the analysis of conditional probabilities of electron density distribution for electron 1 with the reference electron fixed in a certain point 2. It is demonstrated that from the point of view of the mutual coupling of electron motions, the effective pairs behave analogously to singlet pairs. Based on this finding, effective pairs can be interpreted as the fraction of singlet pairs that is directly involved in bonding.

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 Effect of Doping on the Photoelectric Properties of Borophene

2021 ◽  
Vol 2021 ◽  
pp. 1-7
Author(s):  
Chunhong Zhang ◽  
Zhongzheng Zhang ◽  
Wanjun Yan ◽  
Xinmao Qin
Keyword(s):  
Optical Properties ◽  
Band Gap ◽  
Population Analysis ◽  
Covalent Bond ◽  
Infrared Light ◽  
Chemical Bonds ◽  
Mulliken Population Analysis ◽  
Mulliken Population ◽  
Photoelectric Properties ◽  
Effect Of Doping

Borophene is a new type of two-dimensional material with a series of unique and diversified properties. However, most of the research is still in its infancy and has not been studied in depth. Especially in the field of semiconductor optoelectronics, there is no related research on the modulation of photoelectric properties of borophene. In this work, we focus on the effect of doping on the photoelectric properties of borophene by using the first-principles pseudopotential plane wave method. We calculate the geometric structure, electronic structure, Mulliken population analysis, and optical properties of impurity (X = Al, Ga) doped α-sheet borophene. The results show that α-sheet borophene is an indirect band gap semiconductor with 1.396 eV. The band gap becomes wider after Al and Ga doping, and the band gap values are 1.437 eV and 1.422 eV, respectively. Due to the orbital hybridization between a small number of Al-3p electrons and Ga-4p state electrons and a large number of B 2p state electrons near the Fermi level, the band gap of borophene changes and the peak value of the electron density of states reduces after doping. Mulliken population analysis shows that the B0-B bond is mainly covalent bond, but there is also a small amount of ionic bond. However, when the impurity X is doped, the charge transfer between X and B atoms increases significantly, and the population of the corresponding X-B bonds decreases, indicating that the covalent bond strength of the chemical bonds in the doped system is weakened, and the chemical bonds have significant directionality. The calculation of optical properties shows that the static dielectric constant of the borophene material increases, and the appearance of a new dielectric peak indicates that the doping of Al and Ga can enhance the ability of borophene to store electromagnetic energy. After doping, the peak reflectivity decreases and the static refractive index n0 increases, which also fills the gap in the absorption of red light and infrared light by borophene materials. The research results provide a basis for the development of borophene materials in the field of infrared detection devices. The above results indicate that doping can modulate the photoelectric properties of α-sheet borophene.

scholarly journals Novel Insights into the Hydroxylation Behaviors of α-Quartz (101) Surface and its Effects on the Adsorption of Sodium Oleate

Minerals ◽  
2019 ◽  
Vol 9 (7) ◽  
pp. 450 ◽  
Author(s):  
Zhang ◽  
Xu ◽  
Hu ◽  
He ◽  
Tian ◽  
...  
Keyword(s):  
Sodium Oleate ◽  
Density Functional ◽  
Population Analysis ◽  
Water Molecules ◽  
Mulliken Population ◽  
Flotation Reagents ◽  
Functional Theory ◽  
Rigorous Study ◽  
Adsorption Energies ◽  
Hydroxylated Surface

A scientific and rigorous study on the adsorption behavior and molecular mechanism of collector sodium oleate (NaOL) on a Ca2+-activated hydroxylated α-quartz surface was performed through experiments and density functional theory (DFT) simulations. The rarely reported hydroxylation behaviors of water molecules on the α-quartz (101) surface were first innovatively and systematically studied by DFT calculations. Both experimental and computational results consistently demonstrated that the adsorbed calcium species onto the hydroxylated structure can significantly enhance the adsorption of oleate ions, resulting in a higher quartz recovery. The calculated adsorption energies confirmed that the adsorbed hydrated Ca2+ in the form of Ca(H2O)3(OH)+ can greatly promote the adsorption of OL− on hydroxylated quartz (101). In addition, Mulliken population analysis together with electron density difference analysis intuitively illustrated the process of electron transfer and the Ca-bridge phenomenon between the hydroxylated surface and OL− ions. This work may offer new insights into the interaction mechanisms existing among oxidized minerals, aqueous medium, and flotation reagents.

A topological analysis of the interion interactions of tetraphenylphosphonium squarate

2006 ◽  
Vol 84 (5) ◽  
pp. 804-811 ◽  
Author(s):  
David Wolstenholme ◽  
Manuel AS Aquino ◽  
T Stanley Cameron ◽  
Joseph D Ferrara ◽  
Katherine N Robertson
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Electron Density ◽  
Intermolecular Interactions ◽  
Critical Points ◽  
Topological Analysis ◽  
Van Der Waals ◽  
Van Der Waals Interactions ◽  
Multipole Refinement ◽  
Diverse Interactions

The tetraphenylphosphonium squarate salt crystallizes with a number of diverse interactions, which all have the potential to be classified as hydrogen bonds. The squarate anions are found as dimers linked by O-H···O interactions. The multipole refinement of the tetraphenylphosphonium squarate was performed using the Hansen–Coppens model followed by topological analysis of its intermolecular interactions. A total of 28 interactions were found among the symmetry related molecules, which include a number of C-H···Cπ, C-H···O, and C-H···H-C interactions, along with the O-H···O interaction. With the criteria for hydrogen bonding proposed by Popelier and Koch, it is possible to determine which of these interactions are hydrogen bonds and which are van der Waals interactions. Both linear and exponentially dependent correlations can be seen for the properties of the bond critical points involving the intermolecular interactions that fulfill these criteria. All this leads to a better understanding of the role that hydrogen bonds play in the formation of small organic compounds.Key words: electron density, multiple refinement, hydrogen bonds.

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