A comprehensive theoretical study on the bimolecular reaction of C2H502 with OH radicals was performed at the CCSD（T）/6-311＋＋G（2df2p）//B3LYP/6-311＋G（d,p） level of theory. The calculation results show that C2H...A comprehensive theoretical study on the bimolecular reaction of C2H502 with OH radicals was performed at the CCSD（T）/6-311＋＋G（2df2p）//B3LYP/6-311＋G（d,p） level of theory. The calculation results show that C2H5O2 ＋ OH reaction proceeds on both the singlet and the triplet potential energy surfaces（PESs）. On the singlet PES, the favorable pathway is the addition of OH radical to the terminal oxygen atom of C2H5O2 radical, leading to the formation of trioxide C2H5O3H with a barrierless process. Then, the trioxide directly decomposes to the products C2H50 and HO2 radicals. On the triplet PES, the predominant pathways are a and β hydrogen atom abstractions of C2H5O2 radical by OH radical-forming products 3CH3CHO2＋H2O and 3CH2CH2O2＋H2O, and the corresponding bar- tiers are 12.02（3TS8） and 19.19 kJ/mol（3TS9）, respectively. In addition, the comprehensive properties of trioxide C2H503H were investigated for the ftrst time. The results indicate that the trioxide complex RC1 can exist stably in the atmosphere owing to a significantly large and negative enthalpy of formation（-118.44 kJ/mol） as well as a high first excitation energy（5.94 eV）.展开更多
利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 48...利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 4805.1(17) 3, Z = 4, Dc = 2.051 g/cm3, m = 1.431 mm-1, F(000) = 3000, I >2s(I) 的可观察衍射点4426个, 最终结构偏差因子R = 0.0464, wR = 0.0801, S = 0.731。在[P2Mo5O23]6-杂多阴离子中5个MoO6八面体通过共边和共角相连, 形成1个近似的五角平面骨架, 2个PO4四面体加在五角平面的两侧。热性质研究表明杂多阴离子骨架在547.4 ℃左右分解。展开更多
Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of ...Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid （C3H5O）H2SiLi, 1-7, are found. The [2,3]-silawittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the aUyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of SiC（3） bond and the break of O-C（1） bond. Finally, the （allylsilyl）oxylithium （C3H5）H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate （IRC） calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work.展开更多
基金Supported by the National Natural Science Foundation of China（Nos.21473108, 21473107） and the Fundamental Research Funds for the Central Universities of China（No.GK201603035）.
文摘A comprehensive theoretical study on the bimolecular reaction of C2H502 with OH radicals was performed at the CCSD（T）/6-311＋＋G（2df2p）//B3LYP/6-311＋G（d,p） level of theory. The calculation results show that C2H5O2 ＋ OH reaction proceeds on both the singlet and the triplet potential energy surfaces（PESs）. On the singlet PES, the favorable pathway is the addition of OH radical to the terminal oxygen atom of C2H5O2 radical, leading to the formation of trioxide C2H5O3H with a barrierless process. Then, the trioxide directly decomposes to the products C2H50 and HO2 radicals. On the triplet PES, the predominant pathways are a and β hydrogen atom abstractions of C2H5O2 radical by OH radical-forming products 3CH3CHO2＋H2O and 3CH2CH2O2＋H2O, and the corresponding bar- tiers are 12.02（3TS8） and 19.19 kJ/mol（3TS9）, respectively. In addition, the comprehensive properties of trioxide C2H503H were investigated for the ftrst time. The results indicate that the trioxide complex RC1 can exist stably in the atmosphere owing to a significantly large and negative enthalpy of formation（-118.44 kJ/mol） as well as a high first excitation energy（5.94 eV）.
基金PhD Special Research Foundation of Chinese Education Department (No. 20040422010)the Scientific Research Foundation of Yangzhou University
文摘Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid （C3H5O）H2SiLi, 1-7, are found. The [2,3]-silawittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the aUyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of SiC（3） bond and the break of O-C（1） bond. Finally, the （allylsilyl）oxylithium （C3H5）H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate （IRC） calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work.
