1-(4-硝基苯基)-3-(5,6-二甲基-1,2,4三氮唑)-三氮烯质子迁移的理论研究

来源 :计算机与应用化学 | 被引量 : 0次 | 上传用户:mechanical123
下载到本地 , 更方便阅读
声明 : 本文档内容版权归属内容提供方 , 如果您对本文有版权争议 , 可与客服联系进行内容授权或下架
论文部分内容阅读
采用密度泛函B3LYP在6-31G*基组下,对有机显色剂1-(4-硝基苯基)-3-(5,6-二甲基-1,2,4三氮唑)-三氮烯(NPDMTT)的各种可能结构进行质子迁移的3种可能途径:(a)分子内质子迁移,(b)水助质子迁移,(c)甲醇助质子转移的计算,得到了各种途径异构体的相对能,获得了它们的互变异构过程的活化能、活化吉布斯自由能和质子转移反应的速率常数等性质。计算结果表明,分子内质子转移形成的各种异构体相对能量较大,当水分子或甲醇分子参与反应时,异构体的相对能量明显减小,但无论是孤立分子、一水合物还是一甲醇合物,其最稳定的异构体都相同,均为A2。溶剂化效应对异构化能垒的影响较大。最稳定的异构体分子内质子转移在N11和N13间转移的速控步骤的活化能为130.9 kJ.mol-1,反应速度常数为2.172×10-11s-1;当水分子参与反应以双质子转移机理异构化时,活化能显著降低,有利于三氮异构化,其中异构体质子在N11和N13间转移的速控步骤的活化能为22.55 kJ.mol-1,反应速度常数为3.617×107s-1;当醇分子参与反应以双质子转移机理异构时,活化能减小得更多,其中异构体质子在N11和N13间转移的速控步骤的活化能为2.384 kJ.mol-1,反应速度常数为9.032×1011s-1。计算结果还表明,氢键作用在增大NPDMTT一水合物和NPDMTT一甲醇合物相对稳定性、降低质子转移异构化反应活化能等方面起着重要作用。 Under the 6-31G * basis set using density functional theory B3LYP, the organic color reagent 1- (4-nitrophenyl) -3- (5,6-dimethyl-1,2,4 triazole) (A) intramolecular proton migration, (b) water-assisted proton migration, (c) methanol-proton transfer calculations have been obtained for each of the possible structures of triazine (NPDMTT) The relative energy of the pathway isomers, the activation energy of their tautomerization process, the rate constant of activation Gibbs free energy and proton transfer reaction were obtained. The calculated results show that the relative energies of the various isomers formed by intramolecular proton transfer are relatively large, and the relative energies of the isomers are significantly reduced when the water molecules or the methanol molecules are involved in the reaction. However, whether the isolated molecule or the monohydrate is Monomethanol, the most stable isomers are the same, are A2. The effect of solvation on the isomerization barrier is greater. The activation energy of the most stable isomer intramolecular proton transfer in the step-by-step transfer of N11 and N13 is 130.9 kJ · mol-1 and the reaction rate constant is 2.172 × 10-11s-1. When the water molecule participates in the reaction of bis When the proton transfer mechanism isomerization, the activation energy is significantly reduced, which is in favor of tri-isomerization. The activation energy of the isokinetic step in the transfer of the isomeric protons between N11 and N13 is 22.55 kJ · mol-1, the reaction rate constant Was 3.617 × 107s-1. The activation energy decreased more when the alcohol molecule was involved in the bipyramidal mechanism isomerization, and the activation energy of the isokinetic step in the transfer of the isomeric protons between N11 and N13 was 2.384 kJ mol-1, the reaction rate constant is 9.032 × 1011s-1. The calculated results also show that the hydrogen bonding plays an important role in increasing the relative stability of NPDMTT monohydrate and NPDMTT monomethanol and reducing the activation energy of proton transfer isomerization reaction.
其他文献
使用反应型乳化剂烯丙氧基壬基酚聚氧乙烯(10)醚硫酸铵(DNS-86)和常规乳化剂十二烷基硫酸钠(SDS)制备丙烯酸酯乳液,研究了这两种乳化剂对乳液稳定性的影响,比较了两种乳化剂
以α-Keggin型硅钨酸、碳酸铜和2-乙基-3-甲基吡嗪(pyz)为原料,通过水热方法合成了标题化合物.采用元素分析、红外光谱和单晶X-射线衍射法表征了该化合物的结构.晶体结构分析
采用溶胶-凝胶法制备了一系列不同摩尔比K+掺杂的铈锆固溶体xK-Ce0.7Zr0.3O2(x=0.05,0.10,0.15,0.20,0.25,0.30,0.35,0.40),对其催化碳烟颗粒物(PM)燃烧的活性进行了评价,并
群搜索优化算法(Group Search Optimizer,GSO)具有广泛的生物学背景,特别是引入动物的视觉搜索机制,并且同一些已有的群智能算法相比较,在高维多峰问题上有更好的效果.但算法
设L(Rn)表示n维欧氏空间Rn的所有线性变换构成的集合,‖ξ‖表示向量ξ的欧氏长度,由欧氏长度建立起向量间的序关系,令:PO(Rn)={f∈L(Rn)|(A)ξ,η∈Rn×1,‖ξ‖≤‖η‖(→)
利用Taylor公式,Hardy-Littlewood极大函数和Jensen不等式等工具研究了Gamma算子在Orlicz空间内的逼近问题,得出了逼近阶及其逼近等价定理.
对于一维Schr(o)dinger算子,本文基于Simon给出的惟一性定理(势函数由A-函数惟一确定)证明了势函数连续依赖于A-函数;反过来,若势函数q∈L1(0,∞),给出了A-函数也连续依赖于势
超声活化后的竹粉在微波辐射的作用下与丙烯腈反应制备氰乙基化竹粉,考察最佳用量和反应条件对氰乙基化反应的影响,并用电子显微镜、X-射线衍射分析(XRD)、红外(FTIR)和示差
通过润湿分散剂(十二烷基苯磺酸钠ABS-Na、木质素磺酸钠SL和羧甲基纤维素钠CMC)和载体(白炭黑、高岭土)的筛选,确定了60%稀土镧掺杂纳米TiO2可湿性粉剂(WP)的最优配方。试验
采用椭圆偏振光谱技术研究了非晶态碲镉汞薄膜在不同退火条件下的结构性能.结果表明非晶态碲镉汞薄膜在退火过程中的成核晶化是在薄膜内部均匀发生的,对于不同晶化程度的薄膜