The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted add...The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.展开更多
Harmonic vibrational frequencies of hydrazoic acid and methyl azide are calculated using HF. MP2 methods and five popular density functional (DFT) methods and compared with experimental results. Of these seven methods...Harmonic vibrational frequencies of hydrazoic acid and methyl azide are calculated using HF. MP2 methods and five popular density functional (DFT) methods and compared with experimental results. Of these seven methods, BLYP reproduces the observed frequencies most satisfactorily, while the results in HF and MP2 are worse. These indicate the BLYP calculation is a very promising approach for understanding the observed spectral features.展开更多
Harmonic vibrational frequencies of HN3 and CH3N3 molecules and their several isotopomers are calculated using HF, MP2 and five popular density functional theory (DFT) methods. On the basis of the comparison between c...Harmonic vibrational frequencies of HN3 and CH3N3 molecules and their several isotopomers are calculated using HF, MP2 and five popular density functional theory (DFT) methods. On the basis of the comparison between calculated and experimental results, assignments of fundamental vibrational modes are examined. HF and MP2 results are in bad agreement with experimental values. Of the five DFT methods, BLYP reproduces the observed fundamental frequencies the most satisfactorily. Two hybrid DFT methods are found to yield frequencies generally higher than the observed fundamental frequencies. The results indicate that BLYP calculation is a very promising approach for understanding the observed spectral features.展开更多
基金Ⅴ. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.20833008）.
文摘The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.
文摘Harmonic vibrational frequencies of hydrazoic acid and methyl azide are calculated using HF. MP2 methods and five popular density functional (DFT) methods and compared with experimental results. Of these seven methods, BLYP reproduces the observed frequencies most satisfactorily, while the results in HF and MP2 are worse. These indicate the BLYP calculation is a very promising approach for understanding the observed spectral features.
基金Project supported by the Natural Science Foundation of Shandong Province, the National Key Laboratory Foundation of Crystal Material and the National Natural Science Foundation of China (No. 2967305).
文摘Harmonic vibrational frequencies of HN3 and CH3N3 molecules and their several isotopomers are calculated using HF, MP2 and five popular density functional theory (DFT) methods. On the basis of the comparison between calculated and experimental results, assignments of fundamental vibrational modes are examined. HF and MP2 results are in bad agreement with experimental values. Of the five DFT methods, BLYP reproduces the observed fundamental frequencies the most satisfactorily. Two hybrid DFT methods are found to yield frequencies generally higher than the observed fundamental frequencies. The results indicate that BLYP calculation is a very promising approach for understanding the observed spectral features.
