Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show ...Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.展开更多
3,4-Bis（4＇-aminofurazano-3＇）furoxan（DATF）, one of a new generation of high energy density materials, shows lots of interesting properties such as lower sensitivity, excellent thermal stability and superior deton...3,4-Bis（4＇-aminofurazano-3＇）furoxan（DATF）, one of a new generation of high energy density materials, shows lots of interesting properties such as lower sensitivity, excellent thermal stability and superior detonation perfor- mance in chemistry and physics. In this paper, on-line infrared（IR） spectroscopy was used to monitor the synthesis process of DATF. The concentration profiles and IR spectra of the components were determined by analyzing the IR data via principal component analysis（PCA）, evolving factor analysis（EFA） and multivariate curve resolution-alternating least squares（MCR-ALS）. The geometric configurations of reactant, intermediates and product were optimized with the density functional theory（DFT） at B3LYP/6-3 l＋G（d, p） level. Their vibrational frequencies and IR spectra were obtained on the basis of vibrational analysis. The result obtained by the chemometric resolution methods agreed well with that obtained by quantum chemical calculation method, which demonstrated the reliability of the proposed chemometric resolution methods. The unstable intermediate 3-amino-4-oxycyanofurazan（AOF） was confirmed via comparing the IR spectra resloved by chemometric resolution methods with those calculated by B3LYP/6-3 l＋G（d,p） and analyzed by MCR-ALS. Finally, the possible synthesis mechanism of DATF was deduced by analyzing the above IR spectra.展开更多
文摘Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.
基金Supported by the National Natural Science Foundation of China（No.21175106） and the Specialized Research Fund for the Doctoral Program of Higher Education, China（No.20126101110019）.
文摘3,4-Bis（4＇-aminofurazano-3＇）furoxan（DATF）, one of a new generation of high energy density materials, shows lots of interesting properties such as lower sensitivity, excellent thermal stability and superior detonation perfor- mance in chemistry and physics. In this paper, on-line infrared（IR） spectroscopy was used to monitor the synthesis process of DATF. The concentration profiles and IR spectra of the components were determined by analyzing the IR data via principal component analysis（PCA）, evolving factor analysis（EFA） and multivariate curve resolution-alternating least squares（MCR-ALS）. The geometric configurations of reactant, intermediates and product were optimized with the density functional theory（DFT） at B3LYP/6-3 l＋G（d, p） level. Their vibrational frequencies and IR spectra were obtained on the basis of vibrational analysis. The result obtained by the chemometric resolution methods agreed well with that obtained by quantum chemical calculation method, which demonstrated the reliability of the proposed chemometric resolution methods. The unstable intermediate 3-amino-4-oxycyanofurazan（AOF） was confirmed via comparing the IR spectra resloved by chemometric resolution methods with those calculated by B3LYP/6-3 l＋G（d,p） and analyzed by MCR-ALS. Finally, the possible synthesis mechanism of DATF was deduced by analyzing the above IR spectra.
