The hydrolysis of 1,2-thiazetidine 1,1-dioxide has been studied by using ab initio and density functional theory at HF/6-31G*, MP2/6-31G* and B3LYP/6-31G* levels, showing there exist two potential theoretical products...The hydrolysis of 1,2-thiazetidine 1,1-dioxide has been studied by using ab initio and density functional theory at HF/6-31G*, MP2/6-31G* and B3LYP/6-31G* levels, showing there exist two potential theoretical products. One is N-ethyl amino-methyl sulfonate (P1) in which breaking of bond S–C is concerted, the other is 2-taurine methyl ester (P2) which involves two reaction processes with two different mechanisms: concerted and stepwise. There are two pathways of a and b in stepwise, and the former is the lowest in energy barrier in the hydrolysis of 1,2-thiazetidine 1,1-dioxide. The energy barriers of water-assisted hydrolysis of 1,2-thiazetidine 1,1-dioxide are obviously lower than those of no-water-assisted hydrolysis. Solvent effects have been considered by means of a polarizable continuum model (PCM).展开更多
The chemisorption intensities of NH_3 and CO on aluminum clusters A1_n(n=l-13) have been theoretically predicted by using CNDO/2 method and properly selecting the clusters' geometries.The results show that the che...The chemisorption intensities of NH_3 and CO on aluminum clusters A1_n(n=l-13) have been theoretically predicted by using CNDO/2 method and properly selecting the clusters' geometries.The results show that the chemisorptions of NH_3 and GO on Al_2,Al_6 and Al_12 are magically stable and thus are in good agreement with the experimental results.In addition,an electronic structure analysis is made to expound the nature of such a size effect.展开更多
The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crys...The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and luminescence. Chemical formula： C14 H10 N3 O5 Zn1.5. It crystallizes in the monoclinic system, space group P21/c with a = 12.303（4）, b = 12.052（4）, c = 10.212（3） ？, β = 104.147（4）, V = 1468.3（8） ？3, Z = 4, Mr = 398.30, Dc = 1.802 g/cm3, F（000） = 800, μ = 2.501 mm-1 and S = 1.000. The 2-D network architecture of 1 is constructed from benzimidazole, zinc and pyridine-2,3-dicarboxylic acid. The quantum-chemical calculations have been performed on ‘molecular fragments’ extracted from the crystal structure using the B3 LYP method in Gaussian 09. The luminescence spectrum shows that complex 1 emits blue luminescence.展开更多
基金Project supported by the National Natural Science Foundation of China (No. 20373034)
文摘The hydrolysis of 1,2-thiazetidine 1,1-dioxide has been studied by using ab initio and density functional theory at HF/6-31G*, MP2/6-31G* and B3LYP/6-31G* levels, showing there exist two potential theoretical products. One is N-ethyl amino-methyl sulfonate (P1) in which breaking of bond S–C is concerted, the other is 2-taurine methyl ester (P2) which involves two reaction processes with two different mechanisms: concerted and stepwise. There are two pathways of a and b in stepwise, and the former is the lowest in energy barrier in the hydrolysis of 1,2-thiazetidine 1,1-dioxide. The energy barriers of water-assisted hydrolysis of 1,2-thiazetidine 1,1-dioxide are obviously lower than those of no-water-assisted hydrolysis. Solvent effects have been considered by means of a polarizable continuum model (PCM).
文摘The chemisorption intensities of NH_3 and CO on aluminum clusters A1_n(n=l-13) have been theoretically predicted by using CNDO/2 method and properly selecting the clusters' geometries.The results show that the chemisorptions of NH_3 and GO on Al_2,Al_6 and Al_12 are magically stable and thus are in good agreement with the experimental results.In addition,an electronic structure analysis is made to expound the nature of such a size effect.
基金Supported by the Jilin Province Science and Technology Development Plan Item(No.20140204080GX)the Project of the Education Department of Jilin Province,China(No.JJKH20180777KJ)the Science and Technology Development Projects of Siping City(No.2017057)
文摘The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and luminescence. Chemical formula： C14 H10 N3 O5 Zn1.5. It crystallizes in the monoclinic system, space group P21/c with a = 12.303（4）, b = 12.052（4）, c = 10.212（3） ？, β = 104.147（4）, V = 1468.3（8） ？3, Z = 4, Mr = 398.30, Dc = 1.802 g/cm3, F（000） = 800, μ = 2.501 mm-1 and S = 1.000. The 2-D network architecture of 1 is constructed from benzimidazole, zinc and pyridine-2,3-dicarboxylic acid. The quantum-chemical calculations have been performed on ‘molecular fragments’ extracted from the crystal structure using the B3 LYP method in Gaussian 09. The luminescence spectrum shows that complex 1 emits blue luminescence.
