聚醚醚酮链结构与反应的模型化合物的量子化学研究

利用ＡＭ１方法对聚醚醚酮模型化合物全优化，结果为：芳环平均相互扭转角为３３．０度，桥键角１１７．０－１１８．０度，其分子结构拓扑图形表明：所有苯环（核）为平面构型，但其内角扭曲；其氢原子对苯环构型无实质性贡献，在更长链的计算中，冻结苯核与氢原子也得出满意结果，根据Ｍｕｌｌｉｋｅｎ键序与电荷讨论了醚交换与磺化反应。     

Electronic structure and conformational flexibility of 1,4-dihydroazines and their 4-ylide derivatives

The conformational flexibility of 1,4-dihydropyridine, 1,4-dihydropyrimidine, 1,4-dihydropyridazine, 1,4-dihydro-1,3,5-triazine, and their 4-oxo, imino, and methylene derivatives was studied by the semiempirical quantum-chemical AM1 method. It was demonstrated that the replacement of the methylene group in the dihydroazine ring by the exocyclic double bond results only in an increase in the rigidity of the heterocycle rather than leading to a loss of its conformational flexibility. It was suggested that nonplanar conformations of rings in ylide derivatives are stabilized by the nonaromatic cyclic -system. Introduction of the exocyclic double bond does not cause a substantial change in the -electronic structure of the heterocycle. The aromaticity indicesI ₆ andI ₆() were calculated. The correlation between these indices and a change in the energy upon bending of the heterocycle was established.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 8 pp 1938–1941, August, 1996.     

有机光功能材料分子设计研究Ⅰ.俘精酸酐类光致变色材料量子化学研究

用AM1对呋喃基取代的六种俘精酸酐类分子开环体、闭环体基态与激发态的结构进行了优化,所得俘精酸酐1的开环体基态平衡几何结构与已有的实验结果一致.计算结果能较好地解释俘精酸酐的热稳定性和光致变色性能,对取代基对俘精酸酐结构的影响取得了一些新的认识.根据俘精酸酐1开环体上各碳原子的净电荷密度,讨论了它的~(13)CNMR波谱.     

Mechanism of the interaction of color reagent 1,3-N, N'-bis-4-(4'-nitro benzenediazo) phenyl squaraine with oxoacid anions

By AM1 method, the interactions between 1, 3-N, N′-Bis-4-(4′-nitro benzenediazo) phenyl squaraine (BNBPS) and several oxoacid anions have been studied on the basis of the proposed model. The mechanism of the color reactions is suggested and the answers to the question of whether or not BNBPS colorates with HCO_3~-, CO_3~(2-), NO_2~(-), NO_3~-, etc. are given. It is theoretically predicted that BNBPS might be used as the color reagent for SO_4~(2-).     

Theoretical Study of the C_(60)O_3 Isomers

WiththepreparationandisolationofC,,O.'moreandmoreattentionwaspaidtotheirstructuresandpropertiest').WooddetectedC,,O.firstwhentheypreparedC,,byvaporizinggraphite").Fromthenon,thelaboratoriesallovertheworldhavepreparedC6,O.byvariousmethodssuchasPhotoxidationt2-4),Electrochemicaloxi-dation[si,Ozonizationt7.83andChemicaladditiont6'12-14iandsoon.Accordingtothefollow-uptheoreticalstudiesforC,,O.,itisindicatedthattherearetwoisomersofC,,O:eithertheoxygenatomislocatedoverthe6/6bondtogeneratethe6/…     

C70O2可能异构体的结构和电子光谱的理论研究＊

用AM1、 PM3及INDO系列方法研究了C     

卤素及三卤甲基侧取代氮、硫杂冠化合物的电子结构

用ＡＭ１ 方法计算了２０ 个卤素及三卤甲基侧取代氮、硫杂冠化合物分子的电子结构。结果表明,这类杂冠化合物分子的总能量,最高占据分子轨道能量,杂冠醚环中氧、氮原子的电荷分布和空腔大小呈现出一定的规律性。它们对于络合过渡金属具有较强的选择性。     

单重态二碘代乙叉重排反应的AM1方法研究

采用量子化学中的ＡＭ１方法研究了单重态二碘代乙叉重排反应的机理。结果发现,该重排反应经过一个三元环过渡态,反应的能势为２５．８ｋＪ／ｍｏｌ。根据计算结果,详细研究了该反应的热力学及动力学函数,结果表明该反应是放热反应,放出的热量约为２５０ｋＪ／ｍｏｌ;该反应的Ａ因子稍小于１０１３ｓ－１,是典型的单分子反应。由于反应的平衡常数和速度常数都很大,故Ｉ２Ｃ＝Ｃ：一旦生成就立即转变为ＩＣ≡ＣＩ。     

Additive manufacturing for energy storage: Methods,designs and material selection for customizable 3D printed batteries and supercapacitors

Additive manufacturing and 3D printing in particular have the potential to revolutionize existing fabrication processes, where objects with complex structures and shapes can be built with multifunctional material systems. For electrochemical energy storage devices such as batteries and supercapacitors, 3D printing methods allows alternative form factors to be conceived based on the end use application need in mind at the design stage. Additively manufactured energy storage devices require active materials and composites that are printable, and this is influenced by performance requirements and the basic electrochemistry. The interplay between electrochemical response, stability, material type, object complexity and end use application are key to realising 3D printing for electrochemical energy storage. Here, we summarise recent advances and highlight the important role of methods, designs and material selection for energy storage devices made by 3D printing, which is general to the majority of methods in use currently.