Theoretical Study and NBO Analysis of the Decomposition Kinetics of Oxetane, 2-Methyloxetane and 2,2-Dimethyloxetane

A theoretical study of the thermal decomposition kinetics of oxetane (1), 2-methyloxetane (2), and 2,2-dimethyloxetane (3) has been carried out at the B3LYP/6-311+G**, B3PW91/6-311+G**, and MPW1PW91/6-311+G** levels of theory. The MPW1PW91/6-311+G** method was found to give a reasonable good agreement with the experimental kinetics and thermodynamic parameters. The decomposition reaction of compounds 1～3 yields formaldehyde and the corresponding substituted olefin. Based on the optimized ground state geometries using MPW1PW91/6-311+G** method, the natural bond orbital (NBO) analysis of donor-acceptor (bond-antibond) interactions revealed that the stabilization energies associated with the electronic delocalization from σC3-C4 bonding to σ*O1-C2 antibonding orbitals decrease from compounds 1 to 3. The σC3-C4→σO1-C2 resonance energies for compounds 1～3 are 2.63, 2.59 and 2.45 kcal mol-1, respectively. Further, the results showed that the energy gaps between σC3-C4 bonding and σ*O1-C2 antibonding orbitals decrease from compounds 1 to 3. Also, the decomposition process in these compounds are controlled by σ→σ* resonance energies. Moreover, the obtained order of energy barriers could be explained by the number of electron-releasing methyl groups substituted to the Csp3 atom (which is attached to oxygen atom). NBO analysis shows that the occupancies of σCsp3-O bonds decrease for compounds 1～3 as 3<2<1, and those of σCsp3-O bonds increase in the opposite order (3 > 2 > 1). This fact illustrates a comparatively easier thermal decomposition of the sCsp3-O bond in compound 3 compared to compound 2, and in compound 2 compared to compound 1. NBO results indicate that these reactions are occurring through a concerted and asynchronous four-membered cyclic transition state type of mechanism.     

2011年高考江苏卷18题的解法探析与推广

2011年高考江苏卷第18题为：考题如图1，在平面直角坐标系xOy中，M、N分别是椭圆x^2/4＋y^2/2=1的顶点，过坐标原点的直线交椭圆于P、A两点，其中P在第一象限，过P作z轴的垂线，垂足为C，连接AC，并延长交椭圆于点B，设直线PA的斜率为k．     

问题征解

本栏目精选适合高中学生的有趣、实用、新颖、灵巧、深浅适度、富有启发性的题目进行征解,使其成为启迪思维、开发智力的小智囊.该栏目面向广大读者征集问题,问题的选题范围不做限制,但难度应适当控制,适宜高中学生解答.欢迎自编新问题,也可以在现有问题基础上进行改编,提供试题时请注明来源,并请附上解题思路分析和详细解答.每期问题征解时间为40天,欢迎广大读者(尤其是高中学生)踊跃提供解答,提供解答时请标明题号.本刊隔两期刊登供题者或读者提供的解答和有价值的推广,并公布前五位(按来稿时间顺序)提供正确解答的读者名单.提供问题或回答问题时,请在信封上注明学生阅读刊《问题征解》字样,也可发送到电子邮箱:shuxuetongxun@yahoo.com.cn.     

金催化剂上脂肪族硝基化合物与醛在氢气中选择还原耦合

采用TiO2上高度分散的金纳米粒子做催化剂，从脂肪族硝基化合物、醛和氢气可高选择性合成硝酮。与碳负载Pt催化剂相比，该催化体系上硝酮的选择性从50%增加到90%。其催化性能可有活性位结构、载体特性和反应条件精确调节。     

物理学咬文嚼字之三十六 Στοιχειαιο

Euclid的《几何原本》同化学术语中的化学计量比都来自希腊语Στοιχεια■ο,反映的是古希腊原子论的精神.     

NdxCo4Sb12化合物的快速合成及其热电性能研究

采用机械合金化和放电等离子烧结(MA-SPS)技术成功合成了NdxCo4Sb12化合物热电材料. 借助于先进的结构和性能表征手段, 系统研究了NdxCo4Sb12化合物成相和热电性能. 实验结果表明, NdxCo4Sb12化合物中稀土Nd的最佳添加量为x=1.0. Nd1.0Co4Sb12化合物具有较高的热电性能, 其中在400 ℃时具有最大ZT值0.265.