Natural Bond Orbital(NBO)Population Analysis,First Order Hyperpolarizabilities and Thermodynamic Properties of Cyclohexanone

The molecular structure of cyclohexanone was calculated by the B3LYP density functional model with 6-31G(d,p)and 6-311++G(d,p)basis set by Gaussian program.The results from natural bond orbital(NBO)analysis have been analyzed in terms of the hybridization of atoms and the electronic structure of the title molecule.The electron density based local reactivity descriptors such as Fukui functions were calculated.The dipole moment(μ)and polarizability(α),anisotropy polarizability(Δα)and first order hyperpolarizability(βtot)of the molecule have been reported.Thermodynamic properties of the title compound were calculated at different temperatures.

LOCATION OF DOUBLE BOND POSITION OF INSECT SEX PHEROMONE BY GC/MS ANALYSIS WITH CHEMICAL IONIZATION

Ozonolysis products of four lepidopteral pheromone were identified by methane CI-MS.The spectra obtained were notably simpler than those of EI-MS,the peak of molecular ion was normally close to the base peak,and the characteristic fragment ions were high in m/z,thereby the interpretation was facilitated.

Investigation of the Substituent Effects on π-Type Pnicogen Bond Interaction

Intermolecular interactions between PH2Cl and Ar–R（R = H,OH,NH2,CH3,Br,Cl,F,CN,NO2） were calculated by using MP2/aug-cc-p VDZ quantum chemical method.It has been shown from our calculations that the aromatic rings with electron-withdrawing groups represent much weaker binding affinities than those with electron-donating groups.The charge-transfer interaction between PH2Cl and Ar–R plays an important role in the formation of pnicogen bond complexes,as revealed by NBO analysis.Nevertheless,AIM analysis shows that the nature of the interactions between PH2Cl and Ar–R is electrostatic,and the interaction energies of the complexes are correlated positively with the electron densities in the bond critical points（BCPs）.RDG/ELF graphical analyses were performed to visualize the positions and strengths of the pnicogen bonding,as well as the spatial change of the electron localization upon the formation of complexes.The π-type halogen bond was also calculated,and it has been revealed that the π-type pnicogen bond systems are more stable than the halogen bond ones.

Quantum Study on the Hydrogen Bonding Interaction of Luteolin-(CH_3OH)_n

The optimized geometries and vibration frequencies of luteolin,methanol and luteolin-（CH3OH）n complexes have been investigated by density functional theory using B3LYP method.Four stable luteolin-CH3OH complexes,six stable luteolin-（CH3OH）2 complexes and four stable luteolin-（CH3OH）3 complexes have been obtained.The theories of atoms in molecules（AIM） and natural bond orbital（NBO） have been used to analyze the hydrogen bonds of these compounds,and their interaction energies corrected by basis set superposition error are between-8.046 and-76.124 kJ/mol.The calculation results indicate strong hydrogen bonding interactions in the luteolin-（CH3OH）n complexes.Then the nuclear magnetic resonance（NMR） and electronic absorption spectrum of luteolin have been calculated,and the results are in agreement with the experimental data.

The Superconductivity in Fe-Based Family of Superconductors and Its Electronic Structure Analysis in Presence of Dopants Rh and Pd

The discovered in 2008 Fe-based superconductors (SC) are a paramagnetic semimetal at ambient temperature and in some cases they become superconductor upon doping. In spite of so many years since its discovery it is still not known the mechanism that leads to superconductivity. The electronic structure study is used for determining key features of the SC mechanism in these materials. The calculations were performed using the modern suite of programs MOLPRO 2021. We performed quantum calculations of a cluster embedded in a background charge distribution that represents the infinite crystal. The Natural Population Analysis was used for determining the charge and spin distribution in the studied materials. As follows from our results, the possible mechanism for superconductivity corresponds to the RVB theory proposed by Anderson for high Tc superconductivity in cuprates.

Study on Welding-Bead Bonding Strength of Laser-Stacking Copper-Aluminum Heterogeneous Electrode Plates

In this paper,two types of copper-aluminum heterogeneous electrode plates are stacked and the finite element analysis(FEA)models of two different laser welding conditions are built by using SYSWELD welding simulation software to calculate the depth of the welding bead and the temperature distribution of the welding surface.Then,the residual stress analysis data of the welded area are exported and the residual stress is applied to the welded specimen for CAE analysis to ensure that the welding bonding strength meets the design target of a shear force of 500 N or higher.The copper-aluminum laser-stacking simulation technique in this paper can be applied to the manufacturing of copper-aluminum heterogeneous laser-welded electrodes and series-connected electrodes of automotive lithium-ion power battery modules,providing an effective analysis method for welding bonding-strength.

Theoretical Study on the Photodegradation Mechanism of Pyrethroid Insecticide Fenvalerate in Water

The photodegradation mechanism of fenvalerate in water has been investigated by density functional theory（DFT）.The geometries of reactants,transition states,intermediates and products are optimized at the B3LYP/6-31G＊ level.The calculated results indicate that the reaction process mainly includes the nucleophilic attack and the substitution reaction by hydroxyl radical to the carbonyl group.By vibrational frequency analysis and intrinsic reaction coordinate（IRC） method,the transition state and its reaction pathway are confirmed.Moreover,the changes of natural population analysis（NPA）,calculated using the Natural bond orbital（NBO） method,are analyzed along with the degradation reaction which can explain the variation of chemical bonds.Additionally,the solvent effect is also investigated and the results show that the reaction preferably takes place in water.

Density Functional Theoretical Study on the Reaction Mechanism of HOCO and Its Radical

In this paper, the reaction mechanism of HOCO with its radical has been investigated deeply by density functional theory（DFT）, while the geometries and harmonic vibration frequencies of the reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311＋＋G＊＊ level. The CCSD（T）/cc-p VQZ method was used to further calculate the single-point energy of each stationary point along the reaction channel. The result shows that channels（b） and（d） via carbon-carbon intermediates are competing with the ones（e）,（f）,（i） and（l） through carbon-oxygen intermediates, and the six channels are dominant for the title reaction to produce HCOOH and CO2. The result also indicates that the hydrogen abstraction from the HOCO radical can be performed quickly by the self-interaction of HOCO in the absence of other radicals or atoms, which indirectly proves for the first time that the ground-state cis-HOCO radical is not decomposed by the tunneling effect. In addition, the charges of natural population analysis（NPA） and the variation of chemical bonds have been analyzed by the Natural Bond Orbital（NBO） method along with the important reaction path.

Catalytic mechanism and bonding analyses of Au–Pd single atom alloy(SAA):CO oxidation reaction

Single-atom catalysts(SACs),including metalmetal-bonded bimetallic ones named single-atom alloys(SAAs),have aroused significant interest in catalysis.In this article,the catalytic mechanism and bonding analysis of CO oxidation reaction on bimetallic gold–palladium(Au–Pd)model of single atom alloy Au37Pd1 are investigated by using quantum chemical calculations.The molecular geometries and adsorbate/substrate binding energies of CO@Au–Pd,O2@Au–Pd and CO/O2@Au–Pd configurations are identified.The core-shell structure is confirmed to be the most stable structure for Au–Pd SAA,where the Pd atom prefers to situate at the core site.Charge transfer from the Pd atom to the Au atoms has been confirmed to stabilize the structure.According to the binding energy and chemical bonding analysis,both CO and O2 prefer to bind to the Pd atom at the hex site with low coordination number.The formation of new co-adsorption species is identified,in which vertical and parallel bridging adsorptions of CO and O2 on the Au–Pd bonds are observed.CO oxidation on Au–Pd SAA is found to be feasible with low energy barriers and follows the Langmuir-Hinshewood(L-H)mechanism.Our work offers insights into the significant role of single atom of the SAAs in catalytic reactions and can provide evidence for designing new SAAs with high-performance catalytic activities.

Structure and Vibrational Spectroscopy of 2-Methylallyl Alcohol

The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH_(2)=C(CH_(3))−CH_(2)−OH).Density functional theory calculations revealed five stable neutral and three stable cationic MAA conformers,respectively.Two neutral MAA conformers are expected to have an O−H…πintramolecular hydrogen bond interaction,based on the structural characterization that the OH group is directed toward the C=C double bond.The IR spectra of both neutral(2700−3700 cm^(−1))and cationic MAA(2500−7200 cm^(−1))were measured,and the anharmonic IR spectra were calculated at the B3LYP-D3(BJ)/def2-TZVPP level.The OH stretching vibration frequency of neutral MAA was observed at 3656 cm−1,slightly lower than those of methanol and ethanol.In contrast,the OH stretching vibration of cationic MAA was red-shifted by about 140 cm^(−1)compared to neutral MAA.The interaction region indicator and natural bond orbital analysis suggest that the O−H…πinteraction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.

Theoretical Study on N-H…O Blue-shifted H-Bond for HNO…H2O2 Complex

A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6-31G（d）, MP2/6-31 ＋ G（d,p）, MP2/6-311 ＋ ＋ G（d,p）, B3LYP/6-31G（d）, B3LYP/6-31 ＋G（d,p） and B3LYP/6-311 ＋ ＋G（d,p） levels. In the H-bond N-H…O, the calculated blue shift of N-H stretching frequency is in the vicinity of 120 cm^-1 and this is indeed the largest theoretical estimate of a blue shift in the X-H…Y H-bond ever reported in the literature. From the natural bond orbital analysis, the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation. For the blue-shifted H-bond N-H…O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N-H stretching frequency was prominently due to the rehybridization of spn N-H hybrid orbital.

Magnetically assisted gas-solid fluidization in a tapered vessel:Part II Dimensionless bed expansion scaling

The article presents an effort to create dimensionless scaling correlations of the overall bed porosity in the case of magnetically assisted fluidization in a tapered vessel with external transverse magnetic field. This is a stand of portion of new branch in the magnetically assisted fluidization recently created concerning employment of tapered vessels. Dimensional analysis based on ＂pressure transform＂ of the initial set of variables and involving the magnetic granular Bond number has been applied to develop scaling relationships of dimensionless groups representing ratios of pressures created by the fluid flow, gravity and the magnetic field over an elementary volume of the fluidized bed. Special attention has been paid on the existing data correlations developed for non-magnetic beds and the links to the new ones especially developed for tapered magnetic counterparts. A special dimensionless variable Xp = （Ar△Dbt）1/3√RgMQ combining Archimedes and Rosensweig numbers has been conceived for porosity correlation. Data correlations have been performed by power-law, exponential decay and asymptotic functions with analysis of their adequacies and accuracies of approximation.