The molecular structure, the Natural Bond orbital (NBO) and the Time Dependent-DFT of both isomers cis or γ-Cl and trans or δ-Cl of RuCl2(L)2, where L stands respectively for 2-phenylazopyridine (Azpy), 2,4-dimethyl...The molecular structure, the Natural Bond orbital (NBO) and the Time Dependent-DFT of both isomers cis or γ-Cl and trans or δ-Cl of RuCl2(L)2, where L stands respectively for 2-phenylazopyridine (Azpy), 2,4-dimethyl-6-[phenylazo]pyridine (Dazpy), 2-[(3,5-dimethylphenyl)azopyridine] (Mazpy) and 2-pyridylazonaphtol (Nazpy) were calculated with DFT method at B3LYP/LANL2DZ level. The prediction of the frontier orbitals (Highest Occupied Molecular Orbital or HOMO and Lowest Unoccupied Molecular Orbital or LUMO) shows that the most active complexes suitable for electronic reactions are admitted to be the trans isomers. Moreover, δ-RuCl2 (Azpy)2 is discovered to react more actively as photo-sensitizer since its energy gap is the minimum. Besides, electronic structures of all complexes through NBO calculation indicate that Ru-N bonds are made of delocalization of occupancies from lone pair orbital of N atoms to the ruthenium. Moreover, Ru was assumed to have almost the same charge regardless the structure of the azopyridine ligands in the complex indicating that the ligands provide only a steric effect that is responsible for the ruthenium’s selectivity. Concerning the transition state, NBO analysis also highlights that the transition LP(Ru) π*(N1-N2) does correspond to t2g?π*(L). This transition is assumed to correspond to Metal to Ligand Charge Transfer (MLCT) that is responsible for the photo-sensitiveness of the metallic complex. Besides, TDDFT calculation of complexes showed that δ-RuCl2(Nazpy)2 displays the largest band during the absorption. For that reason, it is admitted to be the best photosensitizer due to a large system of conjugation provided by Nazpy ligand.展开更多
The molecular structure of(1S,2R)-2-amino-1-phenylpropan^(-1)-ol(abbreviated as 2APPO)conformers have been studied in the gas phase.Natural Bond Orbital Analysis and Non Linear Optical properties of 2APPO have been pe...The molecular structure of(1S,2R)-2-amino-1-phenylpropan^(-1)-ol(abbreviated as 2APPO)conformers have been studied in the gas phase.Natural Bond Orbital Analysis and Non Linear Optical properties of 2APPO have been performed by DFT level of theory using B3LYP/6-311++G(d,p)basis set.The atomic charges,electronic exchange interaction and charge delocalization of the molecule have been performed by Natural Bond Orbital(NBO)analysis,Natural Population Analysis(NPA) and Non Linear Optical(NLO)properties have been constructed at B3LYP/6-311++G(d,p)level to underst and the optical properties.展开更多
A theoretical study of the thermal decomposition kinetics of ethane halides（C2H6-nXn（n = 1～3）;X = F,Cl,Br） has been carried out at the B3LYP/6-31＋＋G＊＊ and B3PW91/631＋＋G＊＊ levels of theory.Among these meth...A theoretical study of the thermal decomposition kinetics of ethane halides（C2H6-nXn（n = 1～3）;X = F,Cl,Br） has been carried out at the B3LYP/6-31＋＋G＊＊ and B3PW91/631＋＋G＊＊ levels of theory.Among these methods and comparison of activation parameters with available experimental values,the B3PW91/6-31＋＋G＊＊ method is in good agreement with the experimental data.The analysis of bond order and natural bond orbital（NBO） charges,bond indexes,and synchronicity parameters suggest the elimination of HX in reactions 1～9（HF：compounds 1～3,HCl：compounds 4～6,and HBr：compounds 7～9） occur through a concerted and slightly asynchronous four-membered cyclic transition state type of mechanism.展开更多
酸性固色粉NBO是粉末型的高效酸性固色剂,可用冷水配制成30%~40%的溶液使用。酸性染料染色锦纶/氨纶混纺织物,经过酸性固色粉NBO固色,其耐皂洗色牢度、耐汗渍色牢度均能提高0.5~2.0级。用酸性荧光玫红Rhodamine B 400%测试酸性固色粉NB...酸性固色粉NBO是粉末型的高效酸性固色剂,可用冷水配制成30%~40%的溶液使用。酸性染料染色锦纶/氨纶混纺织物,经过酸性固色粉NBO固色,其耐皂洗色牢度、耐汗渍色牢度均能提高0.5~2.0级。用酸性荧光玫红Rhodamine B 400%测试酸性固色粉NBO对染色织物颜色的影响,结果显示:荧光玫红锦纶几乎没有色变;荧光玫红锦纶/氨纶混纺织物有轻微色变,但在可接受范围内。展开更多
Ab initio molecular orbital calculations have been used to investigate the thermal decomposition kinetics of 2-chloroethylethyldichlorosilane at the B3LYP/6-311＋G^＊＊,B3PW91/6-311＋G^＊＊,and MPW1PW91/6-311＋G^＊＊ ...Ab initio molecular orbital calculations have been used to investigate the thermal decomposition kinetics of 2-chloroethylethyldichlorosilane at the B3LYP/6-311＋G^＊＊,B3PW91/6-311＋G^＊＊,and MPW1PW91/6-311＋G^＊＊ levels of theory.Among these methods,the results（activation parameters） obtained using the B3LYP/6-311＋G＊＊ level are in good agreement with the available experimental data.The calculated data imply that in the unimolecular β-elimination reactions of the studied compound in the gas phase,the polarization of C（1）-Cl（3） and C（1）-H（4） bonds in the sense of C（1）^δ＋-Cl（3）^δ-and C（1）^δ＋-H（4）^δ-,respectively,is a determining factor in the gas phase elimination reactions 1,2 and 3.Analysis of bond order,natural bond orbital charges,bond indexes,synchro-nicity parameters,and IRC calculations suggest the elimination of 2-chloroethylethyldichlorosilane via reactions 1～3 can be described as concerted and slightly asynchronous.The transition state structures of these reactions are a four-membered cyclic structure.展开更多
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 ...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.展开更多
The spectroscopic properties of the FT-IR and FT-Raman spectra of the 2-[(2,3-dimethylphenyl)amino]benzoic acid(DMPABA)compound have been recorded in the region 4 000~400cm^(-1).The molecular structure,vibrational wav...The spectroscopic properties of the FT-IR and FT-Raman spectra of the 2-[(2,3-dimethylphenyl)amino]benzoic acid(DMPABA)compound have been recorded in the region 4 000~400cm^(-1).The molecular structure,vibrational wavenumbers were calculated using DFT(B3LYP)method with 6-31G(d,p)and 6-311++G(d,p)basis sets.The Geometrical structure,vibrational frequencies,corresponding vibrational assignments of 2-[(2,3-dimethylphenyl)amino]benzoic acid(DMPABA)have been investigated experimentally and theoretically using Gaussian03 software package.The detailed Molecular orbital calculation such as Natural Bond Orbitals(NBO),Natural Population Analysis(NPA)and Mulliken analysis of atomic charges is also calculated.展开更多
The Fourier Transform Infrared and Raman spectra of the L-Alaninium oxalate(LAO)have been recorded and analyzed.The fundamental vibrational wave numbers intensities of vibrational bands and optirmized geometrical para...The Fourier Transform Infrared and Raman spectra of the L-Alaninium oxalate(LAO)have been recorded and analyzed.The fundamental vibrational wave numbers intensities of vibrational bands and optirmized geometrical parameters of the compound were evaluated using DFT(B3LYP)method with 6-31+-G(d,p)basis set.Natural Bond Orbital(NBO)and Natural Population Analysis(NPA)analysis for the LAO compound was carried out.Mulliken population analyses on atomic charges were also calculated.展开更多
The Molecular Structure of 4-Amino-3-phenylbutanoic acid conformers have been studied in the gas phase. Natural Bond Orbital Analysis(NBO) and Mulliken analysis of atomic charges of 4-Amino-3-phenylbutanoic acid have ...The Molecular Structure of 4-Amino-3-phenylbutanoic acid conformers have been studied in the gas phase. Natural Bond Orbital Analysis(NBO) and Mulliken analysis of atomic charges of 4-Amino-3-phenylbutanoic acid have been performed by DFT level of theory using B3 LYP/6-311++G(d,p) basis set. The atomic charges, electronic exchange interaction and charge delocalization of the molecule have been performed by Natural Bond Orbital(NBO) analysis and Natural Population Analysis(NPA) have been constructed at B3 LYP/6-311++G(d,p) level.展开更多
By using loading test and high temperature test, the electric-property stability of NbO anode and metal Nb anode werestudied in comparison. The reason for higher stability of NbO anode was analyzed by thermodynamics a...By using loading test and high temperature test, the electric-property stability of NbO anode and metal Nb anode werestudied in comparison. The reason for higher stability of NbO anode was analyzed by thermodynamics and kinetics. The loading teswas performed in 38% H2SO4 at 85 ℃ and 12 V for 10 d. The high temperature test was carried out at 250 ℃ in air atmosphere fo30 h. It is found that the NbO anode possesses higher ability to restrain crystallization film as compared with metal Nb anode. It isconsidered that, oxygen in NbO anode matrix restrains the migration of oxygen in Nb2O5 anodic oxidation film to matrix, and resultsin that the anodic oxidation film has higher stability.展开更多
文摘The molecular structure, the Natural Bond orbital (NBO) and the Time Dependent-DFT of both isomers cis or γ-Cl and trans or δ-Cl of RuCl2(L)2, where L stands respectively for 2-phenylazopyridine (Azpy), 2,4-dimethyl-6-[phenylazo]pyridine (Dazpy), 2-[(3,5-dimethylphenyl)azopyridine] (Mazpy) and 2-pyridylazonaphtol (Nazpy) were calculated with DFT method at B3LYP/LANL2DZ level. The prediction of the frontier orbitals (Highest Occupied Molecular Orbital or HOMO and Lowest Unoccupied Molecular Orbital or LUMO) shows that the most active complexes suitable for electronic reactions are admitted to be the trans isomers. Moreover, δ-RuCl2 (Azpy)2 is discovered to react more actively as photo-sensitizer since its energy gap is the minimum. Besides, electronic structures of all complexes through NBO calculation indicate that Ru-N bonds are made of delocalization of occupancies from lone pair orbital of N atoms to the ruthenium. Moreover, Ru was assumed to have almost the same charge regardless the structure of the azopyridine ligands in the complex indicating that the ligands provide only a steric effect that is responsible for the ruthenium’s selectivity. Concerning the transition state, NBO analysis also highlights that the transition LP(Ru) π*(N1-N2) does correspond to t2g?π*(L). This transition is assumed to correspond to Metal to Ligand Charge Transfer (MLCT) that is responsible for the photo-sensitiveness of the metallic complex. Besides, TDDFT calculation of complexes showed that δ-RuCl2(Nazpy)2 displays the largest band during the absorption. For that reason, it is admitted to be the best photosensitizer due to a large system of conjugation provided by Nazpy ligand.
文摘The molecular structure of(1S,2R)-2-amino-1-phenylpropan^(-1)-ol(abbreviated as 2APPO)conformers have been studied in the gas phase.Natural Bond Orbital Analysis and Non Linear Optical properties of 2APPO have been performed by DFT level of theory using B3LYP/6-311++G(d,p)basis set.The atomic charges,electronic exchange interaction and charge delocalization of the molecule have been performed by Natural Bond Orbital(NBO)analysis,Natural Population Analysis(NPA) and Non Linear Optical(NLO)properties have been constructed at B3LYP/6-311++G(d,p)level to underst and the optical properties.
文摘A theoretical study of the thermal decomposition kinetics of ethane halides（C2H6-nXn（n = 1～3）;X = F,Cl,Br） has been carried out at the B3LYP/6-31＋＋G＊＊ and B3PW91/631＋＋G＊＊ levels of theory.Among these methods and comparison of activation parameters with available experimental values,the B3PW91/6-31＋＋G＊＊ method is in good agreement with the experimental data.The analysis of bond order and natural bond orbital（NBO） charges,bond indexes,and synchronicity parameters suggest the elimination of HX in reactions 1～9（HF：compounds 1～3,HCl：compounds 4～6,and HBr：compounds 7～9） occur through a concerted and slightly asynchronous four-membered cyclic transition state type of mechanism.
文摘酸性固色粉NBO是粉末型的高效酸性固色剂,可用冷水配制成30%~40%的溶液使用。酸性染料染色锦纶/氨纶混纺织物,经过酸性固色粉NBO固色,其耐皂洗色牢度、耐汗渍色牢度均能提高0.5~2.0级。用酸性荧光玫红Rhodamine B 400%测试酸性固色粉NBO对染色织物颜色的影响,结果显示:荧光玫红锦纶几乎没有色变;荧光玫红锦纶/氨纶混纺织物有轻微色变,但在可接受范围内。
文摘Ab initio molecular orbital calculations have been used to investigate the thermal decomposition kinetics of 2-chloroethylethyldichlorosilane at the B3LYP/6-311＋G^＊＊,B3PW91/6-311＋G^＊＊,and MPW1PW91/6-311＋G^＊＊ levels of theory.Among these methods,the results（activation parameters） obtained using the B3LYP/6-311＋G＊＊ level are in good agreement with the available experimental data.The calculated data imply that in the unimolecular β-elimination reactions of the studied compound in the gas phase,the polarization of C（1）-Cl（3） and C（1）-H（4） bonds in the sense of C（1）^δ＋-Cl（3）^δ-and C（1）^δ＋-H（4）^δ-,respectively,is a determining factor in the gas phase elimination reactions 1,2 and 3.Analysis of bond order,natural bond orbital charges,bond indexes,synchro-nicity parameters,and IRC calculations suggest the elimination of 2-chloroethylethyldichlorosilane via reactions 1～3 can be described as concerted and slightly asynchronous.The transition state structures of these reactions are a four-membered cyclic structure.
文摘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.
文摘The spectroscopic properties of the FT-IR and FT-Raman spectra of the 2-[(2,3-dimethylphenyl)amino]benzoic acid(DMPABA)compound have been recorded in the region 4 000~400cm^(-1).The molecular structure,vibrational wavenumbers were calculated using DFT(B3LYP)method with 6-31G(d,p)and 6-311++G(d,p)basis sets.The Geometrical structure,vibrational frequencies,corresponding vibrational assignments of 2-[(2,3-dimethylphenyl)amino]benzoic acid(DMPABA)have been investigated experimentally and theoretically using Gaussian03 software package.The detailed Molecular orbital calculation such as Natural Bond Orbitals(NBO),Natural Population Analysis(NPA)and Mulliken analysis of atomic charges is also calculated.
文摘The Fourier Transform Infrared and Raman spectra of the L-Alaninium oxalate(LAO)have been recorded and analyzed.The fundamental vibrational wave numbers intensities of vibrational bands and optirmized geometrical parameters of the compound were evaluated using DFT(B3LYP)method with 6-31+-G(d,p)basis set.Natural Bond Orbital(NBO)and Natural Population Analysis(NPA)analysis for the LAO compound was carried out.Mulliken population analyses on atomic charges were also calculated.
文摘The Molecular Structure of 4-Amino-3-phenylbutanoic acid conformers have been studied in the gas phase. Natural Bond Orbital Analysis(NBO) and Mulliken analysis of atomic charges of 4-Amino-3-phenylbutanoic acid have been performed by DFT level of theory using B3 LYP/6-311++G(d,p) basis set. The atomic charges, electronic exchange interaction and charge delocalization of the molecule have been performed by Natural Bond Orbital(NBO) analysis and Natural Population Analysis(NPA) have been constructed at B3 LYP/6-311++G(d,p) level.
文摘By using loading test and high temperature test, the electric-property stability of NbO anode and metal Nb anode werestudied in comparison. The reason for higher stability of NbO anode was analyzed by thermodynamics and kinetics. The loading teswas performed in 38% H2SO4 at 85 ℃ and 12 V for 10 d. The high temperature test was carried out at 250 ℃ in air atmosphere fo30 h. It is found that the NbO anode possesses higher ability to restrain crystallization film as compared with metal Nb anode. It isconsidered that, oxygen in NbO anode matrix restrains the migration of oxygen in Nb2O5 anodic oxidation film to matrix, and resultsin that the anodic oxidation film has higher stability.
