scholarly journals Understanding the isomerization kinetics in the gas phase of a triazole-3-thione derivative: A theoretical approach

2019 ◽  
Vol 84 (9) ◽  
pp. 975-989
Author(s):  
Zahra Kazeminejad ◽  
Abolfazl Shiroudi ◽  
Khalil Pourshamsian ◽  
Farhad Hatamjafari ◽  
Ahmad Oliaey
Keyword(s):  
Lone Pair ◽  
Nbo Analysis ◽  
State Theory ◽  
Ground State Structure ◽  
Energy Profiles ◽  
Kinetic Rate Constants ◽  
Resonance Energies ◽  
Stabilization Energies ◽  
The Stability ◽  
Kinetics Of

The isomerization reactions of the 4-amino-5-methyl-2,4-dihydro- -3H-1,2,4-triazole-3-thione were studied using the B3LYP and M06-2x, as well as the CBS-QB3 theoretical methods. The measured energy profiles were complemented with kinetic rate constants using the transition state theory (TST). Based on the isomers geometries optimized using the CBS-QB3 method, a natural bond orbital (NBO) analysis shows that the stabilization energies of non-bonding lone-pair orbitals [LP(e)S7] to the ?*N2?C3 antibonding orbital increase from isomers 1 to 2. Moreover, the LP(e)S7 ? ?*N2?C3 delocalizations could fairly explain the increase in the occupancies of LP(e)S7 orbitals for isomers 1 and 2 (2 > 1). The studied stabilization energy increases the stability of the ground state structure, and could fairly explain the kinetics of the isomerization reactions 1 and 2 (k2 > k1). NBO results also suggest that the kinetics of these processes are controlled by the LP ??* resonance energies.

scholarly journals Reaction Mechanisms and Kinetics of the O2 Addition Pathways to the Main Thiophene-OH Adduct: A Theoretical Study

2016 ◽  
Vol 41 (4) ◽  
pp. 398-417 ◽  
Author(s):  
Abolfazl Shiroudi ◽  
Michael S. Deleuze
Keyword(s):  
Transition State ◽  
Reaction Mechanisms ◽  
Density Functional ◽  
Transition State Theory ◽  
Branching Ratios ◽  
State Theory ◽  
Energy Profiles ◽  
Kinetic Rate Constants ◽  
Increasing Temperature ◽  
Kinetics Of

Density functional theory, along with the ΩB97XD and UM06-2x exchange-correlation functional, has been used to study the reaction mechanisms and kinetics of the atmospheric oxidation of the main (kinetically dominant) thiophene-OH adduct [C4H4S-OH]• (R1) by molecular oxygen in its triplet electronic ground state. Kinetic rate constants and branching ratios under atmospheric pressure and in the fall-off regime have been calculated by means of transition state theory (TST), variational transition state theory (VTST) and statistical Rice–Ramsperger–Kassel–Marcus (RRKM) theory. In line with the computed energy profiles, the dominant process under both the thermodynamic and kinetic control of the reaction is O2 addition at the C5 position in syn mode. The computed branching ratios indicate that the regioselectivity of the reaction decreases with increasing temperature and decreasing pressure.

A Computational Study of the Conformational Behavior of 2,5-Dimethyl- 1,4-dithiane-2,5-diol and Analogous S and Se: DFT and NBO Study

2020 ◽  
Vol 17 (10) ◽  
pp. 749-759
Author(s):  
Elmira Danaie ◽  
Shiva Masoudi ◽  
Nasrin Masnabadi
Keyword(s):  
Thermodynamic Parameters ◽  
Computational Study ◽  
Structural Parameters ◽  
Nbo Analysis ◽  
Electron Delocalization ◽  
Stereoelectronic Effects ◽  
Conformational Properties ◽  
Molecular Reactivity ◽  
Stabilization Energies ◽  
The Stability

Conformational behaviors of 2,5-dimethyl-1,4-dithiane-2,5-diol (compound 1), 2,5- dimethyl-1,4-dithiane-2,5-dithiol (compound 2) and 2,5-dimethyl-1,4-dithiane-2,5-diselenol (compound 3) were investigated by the B3LYP/6-311+G **, the M06-2X/aug-ccpvdz levels of theory and natural bond orbital NBO analysis. The structures and the structural parameters of the mentioned molecules were optimized by the B3LYP and the M06-2X methods. We assessed the roles and contributions of the effective factors in the conformational properties of the mentioned compounds by means of the B3LYP and M06-2X levels of theory and the NBO interpretations. The stereoelectronic effects of the mentioned molecules were studied using the NBO analysis. The results showed that the stereoelectronic effects were in favor of the (ax,ax) conformers (the most stable conformations), from compound 1 to compound 3; therefore, these effects have impacts on the conformational properties of compounds 1-3, and stabilization energies associated with LP2X→ σ*S1-C2 electron delocalization, where [X= O, S, and Se], for 1-ax, ax conformer has the greatest value between all of the other conformers. Therefore, according to the calculated thermodynamic parameters, the stability of the 1-ax, ax compound was justified by the presence of LP2X→σ*S1-C2 electron delocalization. A molecular orbital explanation was conducted to investigate the correlations between the linear combinations of natural bond orbitals in the HOMOs, LUMOs and the molecular reactivity parameters. There is a direct relationship between the stereoelectronic effects, molecular reactivity and thermodynamic parameters of compounds 1 to 3 as the harder ax, ax conformations with the greater stereoelectronic effects and ΔG(eq-ax) values are more stable than their corresponding eq, eq conformers. Besides frontier molecular orbitals (FMOs), mapped molecular electrostatic potential (MEP) surfaces of conformations of compounds 1 to 3 were investigated.

AIM and NBO analyses on the interaction between SWCNT and cyclophosphamide as an anticancer drug: A density functional theory study

2015 ◽  
Vol 14 (03) ◽  
pp. 1550021 ◽  
Author(s):  
Zahra Felegari ◽  
Majid Monajjemi
Keyword(s):  
Chemical Shift ◽  
Molecular Orbital ◽  
Density Functional ◽  
Energy Gap ◽  
Chemical Shift Anisotropy ◽  
Lone Pair ◽  
Covalent Bond ◽  
Nbo Analysis ◽  
Molecular Structures ◽  
The Stability

In this work, the molecular structures of single-walled carbon nanotube (SWCNT), cyclophosphamide and cyclophosphamide–SWCNT complex were optimized B3LYP/6–31G* level of theory. The nanotube used in this study was a (5,5) SWCNT including 150 C atoms. The NBO analysis showed that the transfer electron can be occurred from the lone pair of oxygen (donor atom) in the cyclophosphamide to the σ* or π* orbitals of the carbon atoms (acceptor atoms) in the SWCNT. The highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) and energy gap (HOMO–LUMO) were calculated for the studied structures and the results indicated the stability of the complex. In addition, the calculated chemical shift isotropy (σ) and the chemical shift anisotropy (Δσ) confirmed the interaction between cyclophosphamide and SWCNT. Also, the results of the atoms in molecule (AIM) theory indicated that the H 145– O 164 bond is a partial covalent bond.

Kinetics of Various 99mTc-Sn-Pyrophosphate Compounds in the Rat

1977 ◽  
Vol 16 (04) ◽  
pp. 157-162 ◽  
Author(s):  
C. Schümichen ◽  
B. Mackenbrock ◽  
G. Hoffmann
Keyword(s):  
Normal Saline ◽  
Half Life ◽  
Compound A ◽  
Short Half Life ◽  
Low Concentrations ◽  
The Stability ◽  
Kinetics Of ◽  
In Vitro Stability

SummaryThe bone-seeking 99mTc-Sn-pyrophosphate compound (compound A) was diluted both in vitro and in vivo and proved to be unstable both in vitro and in vivo. However, stability was much better in vivo than in vitro and thus the in vitro stability of compound A after dilution in various mediums could be followed up by a consecutive evaluation of the in vivo distribution in the rat. After dilution in neutral normal saline compound A is metastable and after a short half-life it is transformed into the other 99mTc-Sn-pyrophosphate compound A is metastable and after a short half-life in bone but in the kidneys. After dilution in normal saline of low pH and in buffering solutions the stability of compound A is increased. In human plasma compound A is relatively stable but not in plasma water. When compound B is formed in a buffering solution, uptake in the kidneys and excretion in urine is lowered and blood concentration increased.It is assumed that the association of protons to compound A will increase its stability at low concentrations while that to compound B will lead to a strong protein bond in plasma. It is concluded that compound A will not be stable in vivo because of a lack of stability in the extravascular space, and that the protein bond in plasma will be a measure of its in vivo stability.

HUMO-LUMO Studies on Methyl Orange Doped ZTS Crystals for Laser Applications

2018 ◽  
Vol 6 (6) ◽  
pp. 362
Author(s):  
G. Suresh ◽  
K. Sambath Kumar ◽  
P. Ambalavanan ◽  
P. Kumaresan
Keyword(s):  
Molecular Electrostatic Potential ◽  
Nbo Analysis ◽  
Inorganic Materials ◽  
Thermo Gravimetric ◽  
Laser Applications ◽  
Charge Delocalization ◽  
Device Applications ◽  
Warming Rate ◽  
The Stability ◽  
Homo Lumo

Zinc Thiourea Sulphate (ZTS), crystal is a magnificent metal natural compound, which consolidates the upsides of both natural and inorganic materials when contrasted and other customary non-linear optical materials and in this way can be utilized as a part of a more extensive scope of uses. Late endeavors at delivering new recurrence transformation materials have concentrated essentially on expanding the extent of the NLO properties that can recurrence twofold low pinnacle control sources, for example, diode lasers.  The thermo gravimetric examination (TGA) and differential warm investigation (DTA) were completed utilizing Seiko warm analyzer at warming rate 20°C/min in air to decide the warm dependability of the compound. ZTS crystals were developed by moderate cooling procedure. This empowers the development of mass gems along all the three bearings at an ideal pH. FTIR examines demonstrate that in the spectra of ZTS there is a move in the recurrence band in the low-recurrence district which uncovers that thiourea shapes sulfur-to-zinc securities in the ZTS crystals. The stability and charge delocalization of the molecule were also studied by natural bond orbital (NBO) analysis. The HOMO-LUMO energies describe the charge transfer takes place within the molecule. Molecular electrostatic potential has been analyzed.  The developments try in extensive scale with this enhanced pH qualities is required to yield mass crystal appropriate for laser combination tests and SHG device applications.

Effect of delocalization of nonbonding electron density on the stability of the M–Ccarbene bond in main group metal-imidazol-2-ylidene complexes: a computational and structural database study

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Samuel Tetteh ◽  
Albert Ofori
Keyword(s):  
Electron Density ◽  
Lone Pair ◽  
Main Group ◽  
Binding Energies ◽  
Electrostatic Model ◽  
Group Metal ◽  
Main Group Metal ◽  
Structural Database ◽  
The Stability ◽  
Lone Pair Electrons

Abstract The M–Ccarbene bond in metal (M) complexes involving the imidazol-2-ylidene (Im) ligand has largely been described using the σ-donor only model with donation of σ electrons from the sp-hybridized orbital of the carbene carbon into vacant orbitals on the metal centre. Analyses of the M–Ccarbene bond in a series of group IA, IIA and IIIA main group metal complexes show that the M-Im interactions are mostly electrostatic with the M–Ccarbene bond distances greater than the sum of the respective covalent radii. Estimation of the binding energies of a series of metal hydride/fluoride/chloride imidazol-2-ylidene complexes revealed that the stability of the M–Ccarbene bond in these complexes is not always commensurate with the σ-only electrostatic model. Further natural bond orbital (NBO) analyses at the DFT/B3LYP level of theory revealed substantial covalency in the M–Ccarbene bond with minor delocalization of electron density from the lone pair electrons on the halide ligands into antibonding molecular orbitals on the Im ligand. Calculation of the thermodynamic stability of the M–Ccarbene bond showed that these interactions are mostly endothermic in the gas phase with reduced entropies giving an overall ΔG > 0.

Modeling of sorption kinetics of U(VI) micro-quantities nanostructured materials with anatase mesoporous structures

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Veniamin Zheleznov ◽  
Aleksey Golikov ◽  
Tatiana Sokolnitskaya ◽  
Sergey Ivannikov
Keyword(s):  
Nanostructured Materials ◽  
Sorption Kinetics ◽  
Uranyl Ion ◽  
Competitive Sorption ◽  
Hydroxyl Groups ◽  
Complex Ions ◽  
The Stability ◽  
Kinetics Of ◽  
Mesoporous Structures ◽  
Ionic Forms

Abstract The sorption kinetics of uranyl ions micro-quantities from fluoride solutions by nanostructured materials with anatase mesoporous structures has been studied. Using the model of competitive sorption of ions and positively charged complexes of uranyl ion on deprotonated hydroxyl groups of an anatase, kinetic curves of changes in the ratio of ionic forms of uranium in solution were calculated. Modeling was carried out under the assumption of a two-stage mechanism of uranium complex ions sorption. The modeling considered the influence of the uranyl ion carbonate complexes formation. The shift in equilibrium among ionic forms of uranyl correlates with the stability of the complexes in solution.

scholarly journals Experimental Study on the Softening Characteristics of Sandstone and Mudstone in Relation to Moisture Content

2017 ◽  
Vol 2017 ◽  
pp. 1-14 ◽  
Author(s):  
Gui-chen Li ◽  
Chong-chong Qi ◽  
Yuan-tian Sun ◽  
Xiao-lin Tang ◽  
Bao-quan Hou
Keyword(s):  
Moisture Content ◽  
Vertical Displacement ◽  
Surface Porosity ◽  
Shear Tests ◽  
Moisture Contents ◽  
Dynamic Finite Element ◽  
Rock Types ◽  
Underground Roadway ◽  
The Stability ◽  
Kinetics Of

The kinetics of fluid-solid coupling during immersion is an important topic of investigation in rock engineering. Two rock types, sandstone and mudstone, are selected in this work to study the correlation between the softening characteristics of the rocks and moisture content. This is achieved through detailed studies using scanning electron microscopy, shear tests, and evaluation of rock index properties during exposure to different moisture contents. An underground roadway excavation is simulated by dynamic finite element modeling to analyze the effect of moisture content on the stability of the roadway. The results show that moisture content has a significant effect on shear properties reduction of both sandstone and mudstone, which must thus be considered in mining or excavation processes. Specifically, it is found that the number, area, and diameter of micropores, as well as surface porosity, increase with increasing moisture content. Additionally, stress concentration is negatively correlated with moisture content, while the influenced area and vertical displacement are positively correlated with moisture content. These findings may provide useful input for the design of underground roadways.

Adhesion of Fine Particles at Solid/Solution Interfaces

MRS Bulletin ◽  
1990 ◽  
Vol 15 (1) ◽  
pp. 41-47 ◽  
Author(s):  
Nikola Kallay
Keyword(s):  
Fine Particles ◽  
Plane Surface ◽  
Solid Surfaces ◽  
Liquid Media ◽  
Latex Dispersions ◽  
Colloid Particles ◽  
The Subject ◽  
Kinetic Investigations ◽  
The Stability ◽  
Kinetics Of

The adhesion of particles at solid surfaces in liquid media has attracted the attention of scientists because of its various applications as well as the theoretical significance of the processes involved. Early studies were characterized either by poorly defined systems or limited by the properties of a few morphologically well-defined model colloids, such as latex dispersions. Consequently, results were either of semiquantitative nature or were related to some specific cases, which eluded general conclusions. New methods for preparing uniform particles of different compositions, shapes, and sizes make it possible to approach the problem in a more comprehensive manner. For example, to demonstrate difficulties caused by polydispersity, it is sufficient to mention that the electrostatic interaction energy between a plane surface and a particle is approximately proportional to the particle radius, yet the rate of deposition depends exponentially on the height of the energy barrier.In principle, static and dynamic approaches may be employed in the study of particle adhesion. The static method yields the force required to detach an adhered particle, while kinetic investigations of attachment and detachment give the rates of the respective processes. Both methods offer information on the stability of the system in terms of the bond strength of adhered solids. For small colloid particles, which are the subject of thermal random Brownian motion, the dynamic approach is more appropriate. This article emphasizes the kinetics of deposition and detachment of small colloid particles in liquid media.

Sign in / Sign up

Export Citation Format

Share Document