Search results for "physical chemistry"
showing 10 items of 1199 documents
Solvent impact on the planarity and aromaticity of free and monohydrated zinc phthalocyanine: a theoretical study
2017
A theoretical investigation on the planarity of molecular structure of zinc phthalocyanine (ZnPc) and its aromaticity has been performed using B3LYP and M06-2X density functionals combined with selected Pople-type basis sets. The effect of the applied calculation method on the optimized structure of ZnPc and ZnPc∙∙∙H2O, both in the gas phase and in the polar solvent, was analyzed. To quantify the aromaticity of the ZnPc and ZnPc∙∙∙H2O complexes, both the geometric and magnetic criteria, i.e., Harmonic Oscillator Model of Aromaticity (HOMA) index and the nucleus-independent chemical shift (NICS) values at the centers or 1 A above the centers of structural subunits, were calculated. The energ…
3 He NMR studies on helium-pyrrole, helium-indole, and helium-carbazole systems: a new tool for following chemistry of heterocyclic compounds
2014
The 3He nuclear magnetic shieldings were calculated for free helium atom and He–pyrrole, He–indole, and He–carbazole complexes. Several levels of theory, including Hartree–Fock (HF), Second-order Moller-Plesset Perturbation Theory (MP2), and Density Functional Theory (DFT) (VSXC, M062X, APFD, BHandHLYP, and mPW1PW91), combined with polarization-consistent pcS-2 and aug-pcS-2 basis sets were employed. Gauge-including atomic orbital (GIAO) calculated 3He nuclear magnetic shieldings reproduced accurately previously reported theoretical values for helium gas. 3He nuclear magnetic shieldings and energy changes as result of single helium atom approaching to the five-membered ring of pyrrole, indo…
Heptane Adsorption in Silicalite-1: Neutron Scattering Investigation
2007
International audience; Structural properties of confined deuterated n-heptane in silicalite-1 have been investigated by neutron scattering experiments during the adsorption process. At 300 K, the adsorption isotherm shows a sharp inflection at a loading near Nads ) 4 molecules per silicalite-1 unit cell. In addition, the diffusivities obtained from recent QENS data exhibit a loading dependence. Our motivation is to find structural signatures of the peculiar behavior of n-heptane in silicalite-1 and to check the numerous computer simulation findings of this behavior. Our detailed neutron diffraction investigation agrees with the MONO-ORTHO phase transition of the silicalite-1 above a Nads v…
Calorimetric investigation on the formation of palladium nanoparticles in water/AOT/n-heptane microemulsions
1995
The formation enthalpy of palladium nanoparticles in water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT)n-heptane microemulsions as a function of the waterAOT molar ratio (R = [water][AOT]) was measured by a calorimetric technique. The results indicate that at R < 10 the energetic state of the palladium nanoparticles compartmentalized within the reversed AOT micelles is signficantly different from that in bulk water. Effects due to the small size of the palladium nanoparticles and to interactions between nanoparticles and the waterAOT interface are discussed.
Hydrocracking ofn-heptane with a NiO-MoO3/HYUS zeolite as catalyst. Kinetic study
1988
The hydrocracking of n-heptane has been carried out in a fixed bed reactor at 2.45 MPa pressure and with a H2/n-heptane molar ratio of 5.0 using a 4 wt% NiO - 8 wt% MO3/HYUS zeolite as a catalyst. The W/F10 ratio was varied between 75.3 and 1624 kg · s/kmol at different reaction temperatures: 573, 588, 603 and 623 K. The kinetics of the reaction has been studied by two different procedures due to the slight deactivation of the catalyst. One of them uses the conversion and yield values extrapolated at time on stream to zero and the other uses a kinetic equation where the deactivation of the catalyst has been included. The experimental data were fit well by a pseudo-first order kinetic equati…
p -Type and n -type conductometric behaviors of octachloro-metallophthalocyanine-based heterojunctions, the key role of the metal
2020
In the present work, we determined the electrical properties of octachlorinated metallophthalocyanines with Co(II) and Cu(II) ions as metal centers. We engaged them in heterojunctions, with lutetium bisphthalocyanine as a partner. Surprisingly, cobalt and copper complexes show opposite behaviors, the first being an [Formula: see text]-type material whereas the latter is a [Formula: see text]-type material, as deduced from the response of the heterojunctions towards ammonia; showing the unusual key role played by the metal center. While the LuPc[Formula: see text]/Cu(Cl[Formula: see text]Pc) complex exhibits a negative response to ammonia, the LuPc[Formula: see text]/Co(Cl[Formula: see text…
Microstructure-process relationship and reactivity at the nanoscale : a molecular dynamics study of Ni, Ni-Al, and Ti-Al metallic systems
2023
The process-microstructure relationship is central in materials science because the microstructure will determine the properties of the materials developed by the processes. In our work, we focused on different metallurgical processes by adopting a description at the atomic scale. This approach allows us to detect the elementary mechanisms that are at the origin of the observed microstructures without having to postulate macroscopic mechanisms or estimate the associated parameters. In this respect, molecular dynamics simulations provide a tool for "in-situ" observation of metallic systems as long as an atomic interaction potential is available. The originality of our approach consists in mo…
Inclusion complexes of triphenylphosphine derivatives and peracetylated-β-cyclodextrin in supercritical carbon dioxide
2008
The supramolecular chemistry of peracetylated-β-CD (perAc-β-CD) as a host for triphenyphosphine derivatives has been studied in supercritical (scCO2) using UV absorption spectroscopy. It was found that the association constant in scCO2 at 40°C and 300 bar is 10 to 1000 times smaller compared to analogous systems in aqueous solvent. Studies of the thermodynamics of the inclusion process found an enthalpy of association of -30 kJ/mole and an entropy of -55 J/moleK. This difference with respect to water is attributed to the absence of the hydrophobic effect in scCO2 due to the much smaller polarity of scCO2 versus water. To further explore the effect of the solvent on the association constant,…
Theoretical investigations of nitrogen doping on Co 3 O 4 for water dissociation catalytically activity
2018
We report the results of theoretical investigations of nitrogen doping on Co 3 O 4 (100) bulk by means of the plane-wave periodic density functional theory (DFT) calculations combined with the Hubbard-U approach and statistical thermodynamics.Using accurate DFT+U calculations, we have shown that bulk Co ions denote charges in value 0.017 - 0.57e. For further water adsorption process studies was selected structures with most changes in charges in Co ions: (3) structure for n = 25%, (2) structure forn = 12.5% and structure for (1) structure.
Transition levels of acceptor impurities in ZnO crystals by DFT-LCAO calculations
2018
This research was partly supported by the Kazakhstan Science Project № AP05134367«Synthesis of nanocrystals in track templates of SiO2/Si for sensory, nano-and optoelectronic applications» and Latvian Super Cluster (LASC), installed in the Institute of Solid State Physics (ISSP) of the University of Latvia. Authors are indebted to D. Gryaznov, A. Popov and A. Dauletbekova for stimulating discussions.