N6H6结构和性质的理论研究

采用密度泛函理论的b3lyp方法在6-311＋＋G**基组上对15种分子式为N₆H₆的氮氢化合物进行了理论计算, 并且应用了自然键轨道理论(Nature Bond Orbital, NBO)和分子中的原子理论(Atoms In Molecules, AIM)分析了这些化合物的成键特征和相对稳定性. NBO分析表明N原子孤对电子到相邻的氮氮键的超共轭作用是影响氮氮键长变化的主要因素, AIM计算的氮氮键的键临界点电荷密度与键长呈反比关系. 而且, NBO的立体和超共轭分析表明立体交换排斥能和超共轭作用对这些分子的相对稳定性起了重要作用. G3MP2计算结果表明氮氢化合物的生成热均为正, 并且环状分子的能量和生成热都高于链状分子.     

N6H6结构和性质的理论研究

采用密度泛函理论的b3lyp方法在6-311＋＋G**基组上对15种分子式为N₆H₆的氮氢化合物进行了理论计算, 并且应用了自然键轨道理论(Nature Bond Orbital, NBO)和分子中的原子理论(Atoms In Molecules, AIM)分析了这些化合物的成键特征和相对稳定性. NBO分析表明N原子孤对电子到相邻的氮氮键的超共轭作用是影响氮氮键长变化的主要因素, AIM计算的氮氮键的键临界点电荷密度与键长呈反比关系. 而且, NBO的立体和超共轭分析表明立体交换排斥能和超共轭作用对这些分子的相对稳定性起了重要作用. G3MP2计算结果表明氮氢化合物的生成热均为正, 并且环状分子的能量和生成热都高于链状分子.     

N8H8环状异构体的结构与稳定性的理论研究

采用密度泛函理论的B3LYP方法在6-311 G**基组水平上对N8H8氮氢环状化合物可能存在的构型进行了几何优化,得到74种稳定异构体,应朋A然键轨道理论NBO和分子中的原子理论AIM分析了这些化合物成键特征和相对稳定性,G3MP2方法汁算了各异构体的能量及生成热.研究结果表明:N原子孤对电子到相邻的氮氮键的超共轭作用是影响氮氮键长变化的丰要因素;N8H8环状异构体的稳定性顺序为:六元环>七元环>八元环,五元环>三元环>四元环,六元环是这些N8H8环状异构体中最稳定的,最不稳定的是四元环,G19是所有环状异构体中能量最低的:M3能量最高,稳定性最差,A7密度最大.     

N8H8环状异构体的结构与稳定性的理论研究

采用密度泛函理论的B3LYP方法在6-311＋＋G**基组水平上对N₈H₈氮氢环状化合物可能存在的构型进行了几何优化, 得到74种稳定异构体, 应用自然键轨道理论NBO和分子中的原子理论AIM分析了这些化合物成键特征和相对稳定性, G3MP2方法计算了各异构体的能量及生成热. 研究结果表明: N原子孤对电子到相邻的氮氮键的超共轭作用是影响氮氮键长变化的主要因素; N₈H₈环状异构体的稳定性顺序为: 六元环＞七元环＞八元环, 五元环＞三元环＞四元环, 六元环是这些N₈H₈环状异构体中最稳定的, 最不稳定的是四元环, G19是所有环状异构体中能量最低的; M3能量最高, 稳定性最差, A7密度最大.     

1,2,4,5-四嗪含氮取代基衍生物结构和性质的理论研究

在B3LYP/aug-cc-pvDZ理论水平上研究了CN,NO2,NH2,N3,N2H,NHNH2,N4H和N4H3含氮取代基取代1,2,4,5-四嗪环上的两个氢原子生成的衍乍物,预测了它们的分f构犁、分解能及含能性质.对衍生物分解能的研究结果表明.CN取代的衍生物的分解能比未取代时更高,而其余基团的取代使分解能降低.生成热的研究显示取代基化合物的生成热越大,取代1,2,4,5-四嗪中的氢原子后生成衍生物的牛成热也越大;CN,N3和N4H取代的1,2,4,5-四嗪衍生物的单位原子生成热在83.1～95.2 kJ,比文献报道的三叠氮基-均三嗪的(70.2 kJ)更高;N4H,N3,N4H3,N2H和CN取代的1,2,4,5-四嗪衍生物,生成热在904.9～1496.6 kJ·mol-1,但N4H和N4H3取代的衍生物分解能较小,稳定性较差.     

先锋褐煤可溶有机质中含氮化合物的组成和结构特征（英文）

先锋褐煤在高压釜中用等体积的甲醇/甲苯溶剂300℃下热溶得到热溶物和热溶残渣,利用X射线光电子能谱(XPS)分析了先锋褐煤及其热溶残渣中氮的形态,利用气相色谱/质谱(GC/MS)和电喷雾傅里叶变换-离子回旋共振质谱(ESI FT-ICR MS)分析了热溶物中含氮化合物的组成和结构特征。研究表明,先锋褐煤中氮形态含量顺序为季氮吡啶氮吡咯氮,而季氮在热溶过程中更易溶出。GC/MS共检测出热溶物中20种含氮化合物,并且大部分为胺类化合物。ESI FT-ICR MS检测出热溶物中300多种含氮化合物,大部分含氮化合物含一个或三个氮原子。含一个氮原子的含氮化合物主要以N_1O_1、N_1O_2和N_1O_xS_(1-2)类化合物为主,而含三个氮原子的含氮化合物主要以N_3O_xS_(1-2)(x=1-12)类化合物为主。含一个氮原子的含氮化合物的等效双键数和碳数随氧原子数增加而增加。     

多氯代吩噁嗪热力学性质的密度泛函理论研究

在B3LYP/6-31G*水平上对135个多氯代吩噁嗪(PCPXs)系列化合物进行了全优化和振动分析计算, 得到各分子在298.15 K, 1.013×105 Pa标准状态下的热力学性质. 设计等键反应, 计算了PCPXs系列化合物的标准生成热(Δf )和标准生成自由能(Δf ), 研究了这些参数与氯原子的取代位置及取代数目(NPCS)之间的关系, 结果表明: 熵( )、Δf , Δf 与NPCS之间有很强的相关性. 根据异构体标准生成自由能的相对大小, 从理论上求得异构体的相对稳定性. 以Gaussian 03程序的输出文件为基础, 采用统计热力学程序计算了PCPXs化合物在200 K至1800 K的摩尔恒压热容(Cp,m), 并用最小二乘法求得Cp,m与温度之间的相关方程, 发现Cp,m与T, T－1和T－2之间有着很好的相关性.     

先锋褐煤可溶有机质中含氮化合物的组成和结构特征

先锋褐煤在高压釜中用等体积的甲醇/甲苯溶剂300℃下热溶得到热溶物和热溶残渣,利用X射线光电子能谱（XPS）分析了先锋褐煤及其热溶残渣中氮的形态,利用气相色谱/质谱（GC/MS）和电喷雾傅里叶变换-离子回旋共振质谱（ESI FT-ICR MS）分析了热溶物中含氮化合物的组成和结构特征。研究表明,先锋褐煤中氮形态含量顺序为季氮 > 吡啶氮 > 吡咯氮,而季氮在热溶过程中更易溶出。GC/MS共检测出热溶物中20种含氮化合物,并且大部分为胺类化合物。ESI FT-ICR MS检测出热溶物中300多种含氮化合物,大部分含氮化合物含一个或三个氮原子。含一个氮原子的含氮化合物主要以N₁O₁、N₁O₂和N₁O_xS_1-2类化合物为主,而含三个氮原子的含氮化合物主要以N₃O_xS_1-2（x=1-12）类化合物为主。含一个氮原子的含氮化合物的等效双键数和碳数随氧原子数增加而增加。     

多溴二苯并呋喃的热力学性质和稳定性的密度泛函理论研究

在B3LYP/6-31G*水平上对二苯并呋喃和135个多溴二苯并呋喃系列化合物(PBDF)进行了全优化计算和振动分析, 得到各分子的总能量(E_T)、焓(H⁰)、熵(S⁰)、自由能(G⁰)和恒容热容(C_V⁰), 研究了这些参数与溴原子的取代数目及取代位置的关系. 溴原子置换在不同位置时, 使E_T, H⁰和G⁰数值增加大小次序为: 1(9)＞3(7)＞2(8)＞4(6), 即置换在1(9)位最不稳定; 两个溴原子处在同一苯环时, E_T, H⁰和G⁰数值也都增加, 增加的顺序为: 邻>>间＞对, 即相互处于邻位最不稳定. 而且有两个溴原子同时取代在1和9位时, 使H⁰和G⁰的数值的增加比取代在邻位、间位和对位时的增加值都大. 每增加1个溴原子, S⁰增大约40.1 J•mol^－1•K^－1, C_V⁰增大约16.3 J•mol^－1•K^－1. 同时, 设计等键反应, 计算了各异构体的标准生成热(H_f⁰)和标准生成自由能(G_f⁰). 根据异构体自由能的相对大小, 从理论上求得异构体的相对稳定性顺序, 各异构体组中的稳定性顺序与PCDF系列的稳定性顺序基本一致.     

取代基对螺噁嗪类化合物光致变色性能影响的探究

本文合成了4种螺噁嗪类化合物,并通过FTIR、1H NMR、ESI-MS对其结构进行了表征。研究了吲哚环上氮原子和噁嗪环9′位不同的取代基及溶剂化效应对其光致变色性能的影响。结果表明,吲哚环的氮原子引入体积较大的基团对螺噁嗪最大吸收波长无明显影响,然而有利于开环体的稳定性,且溴原子的引入会影响螺噁嗪的光响应性;噁嗪环9′位上的供电子基团会降低螺噁嗪的开环体稳定性;螺噁嗪开环体的褪色过程符合一级动力学方程;在非质子溶剂中,螺噁嗪开环体的最大吸收波长呈现正向溶剂化效应;有机酸的加入,可以增加开环体的热稳定性。     

Theoretical study of structures and properties of cyclobutadiene, cyclopentadiene and benzene and their nitrogen isoelectronic equivalents

B3LYP/aug-cc-pvDZ level of theory is applied to study the geometric structures, electronic topologies, heats of formation, hyperconjugations and steric repulsions of 27 kinds of compounds obtained by successive replacement of CH groups with nitrogen atoms in cyclobutadiene, cyclopentadiene and benzene. The results reveal that the total energy linearly decreases along with the replacement of CH groups by nitrogen atoms for the three systems. To estimate the potential of high nitrogen content high energy materials (HNC–HEMs), heats of formation are calculated by G3 method. With the increase of the number of nitrogen atoms in ring, heats of formation increase substantially. The four-membered ring system is found to have the greatest heat of formations, followed by the six-membered ring system, and then by the five-membered ring system. Especially, hexazine and tetraazacyclobutadiene have great heats of formation relative to the other compounds, which implies that they should be applicable as HNC–HEMs. In addition, our studies indicate that the relationship between the total energy or heats of formation of isomers and the position of nitrogen atoms is (ortho) meta < (ortho) para < ortho. NBO analysis shows that it is hyperconjugation, not steric repulsion that plays a key role in the relative stability of isomers.     

Theoretical study on the structures and properties of the isomers of Nn(CH)8−nH8 (n = 0–7)

With replacement of N atoms by CH groups in the most stable chain isomer of N8H8, 34 possible isomers of N_n(CH)_8−nH₈ (n = 0–7) have been designed and optimized at the B3LYP/6-311++G** level of theory. The natural bond orbital (NBO) and atoms in molecules (AIM) analysis are carried out to study the bonding nature and relative stabilities of these conformers. G3MP2 method is applied to calculate energies and heats of formation. The results indicate that the hyperconjugation effect from lone pairs of nitrogen atoms to germinal C–N bonds is the major factor which caused the change of the C–N bond length. With the more replacement of nitrogen atoms by CH groups, the heats of formation of the isomers of N_n(CH)_8−nH₈ (n = 0–7) decrease gradually, but the energies increase linearly.     

N_n(CH)_(4-n)H_4(n=0-4)的环状结构与性质的理论研究

由于高能量密度材料HEDM在现代科技工业中的重要意义[1-2],其合成研究及应用也成为21世纪初固体推进剂研制发展的热点.氮氢化合物(NnHm)不稳定,在自然界中存在较少,大多都以反应中间体或裂解产物形式存在,此类化合物在含能材料方面有重要作用,因此人们从上个世纪50年代就开始重视对氮氢化合物的理论和实验的研究[3].     

新型吡啶环液晶化合物的合成及性能

以2-溴-5-吡啶甲醛和5-溴-2-吡啶甲醛为起始原料,合成出4种新型含吡啶环二联芳基和三联芳基化合物,总收率20%~30%。 热性能研究结果表明,二联芳基化合物未呈现出液晶相,而三联芳基化合物在加热和冷却过程中均表现向列相液晶态,且当氮原子位于正丁基的间位时,其与不含氮原子的三联苯化合物(2c)相比,熔点降低了11.7 ℃,清亮点升高6.3 ℃,液晶相区拓宽了18 ℃,表现出了良好的热性能。 光电性能测试结果表明,用吡啶环替代苯环后,化合物的光学各向异性值均较参比化合物(1c或2c)增大;当N原子位于正丁基的邻位的化合物,介电各向异性值较参比化合物增大,且液晶的阈值电压、饱和电压均降低。 通过对三环同分异构体化合物的不同构象能量态的计算分析,解释了介电各向异性的变化规律。     

Theoretical investigation on the replacement of CH groups by N atoms in caged structure (CH)8

A molecular design was performed for the caged molecule (CH)8: the replacement of CH groups by N atoms to increase the content of N as well as reduce the content of H. A series of caged molecules were obtained: (CH)xN(8-x) (0 < or = n < or = 8). The studied aspects are as follows: (i) molecular geometries and electronic structures, (ii) the analysis of the electronic structure using natural bond orbital (NBO) and atoms in molecules (AIM), and (iii) some physicochemical properties of studied molecules, such as the dipole moments, IR vibrational spectra, NMR chemical shifts, heats of formation, and relative specific impulses, were provided. Our studies show that these molecules should be a kind of potential and novel energetic material. Our work provides some useful information for the experimental study of these molecules. The effect of the substitution of N atoms for CH groups on the properties of this kind of caged molecule is presented.     

Theoretical predictive study on N7H7 hydronitrogen compounds

Geometric structures and energy properties of 25 isomers of N₇H₇ hydronitrogen compounds have been studied at the B3LYP/6-311++G(d,p) level. Atoms in molecules (AIM) and nature bond orbital (NBO) theories are applied to analyze the bond nature and the origin of structure and energy variations. The result indicates that the hyperconjugation from the lone pair of nitrogen to the neighboring NN bond plays an important role in the NN bond length variation and the relative stability of the 25 isomers can be attributed to the steric and hyperconjugative effects. G3MP2 calculations show that the heats of formation (HOFs) of all the isomers, especially those of the cyclic isomers, are positive and large, suggesting their potential to be energy molecules. Furthermore, the HOFs of the cyclic isomers decrease with increase of the number of substituents.     

空气稳定的氮杂蔻电子传输材料分子设计及三氮杂蔻衍生物迁移率计算

采用密度泛函理论研究氮功能化对蒄类化合物几何构型、电子结构及载流子传输性质的影响. 结果表明, 引入杂N原子可以线性降低前线轨道能级, 增强电子注入能力与空气稳定性, 且邻位掺杂较迫位和均匀掺杂调节效果更为显著. 其中, 十二氮杂蒄（12ac）具有新颖的“碗状”构型和高的电子亲和势（3.45 eV）, 是潜在的空气稳定电子传输材料构筑单元. 理论预测室温下2,6,10-三对甲氧基苯基-3,4,7,8,11,12-六甲氧基三氮杂蒄（3b）晶体的电子迁移率为0.242 cm2/V s, 预计是良好的电子传输材料, 值得进一步器件化研究.     

1H- and 13C-NMR. Studies of some metal complexes of o,o′-dihydroxyazobenzenes

The aromatic ¹H- and ¹³C-NMR. spectra of some metal complexes of o, o′-dihydroxyazobenzenes are shown to be useful in distinguishing the two possible isomers (acolar and discolar) stemming from the non equivalence of the two ligating azo nitrogen atoms. The ortho aromatic carbon atoms, C(6) and C(12) experience relatively large upfield shifts between 12.8 and 15.7 ppm when the adjacent nitrogen atom is coordinated. The protons attached to these carbon atoms are shifted downfield. The values ⁿJ (¹⁵N, ¹³C) for the ligand 2,2′-dihydroxy-3-methyl-4′-chloro-5-(t-butyl)-¹⁵N-azobenzene are reported.     

Why CH3CH3+* formation competes with H* loss from CCCO C3H6O+* isomers

How formation of CH3CH3+* competes with H* loss from C3H6O+* isomers with the CCCO framework has been a puzzle of gas phase ion chemistry because the first reaction has a substantially higher threshold and a supposedly tighter transition state. These together should make CH3CH3+* formation much the slower of the two reactions at all internal energies. However, the rates of the two reactions become comparable at about 20 kJ x mol(-1) above the threshold for CH3CH3+* formation. It was recently shown that losses of atomic fragments increase in rate much more slowly with increasing internal energy than do the rates of competing dissociations to two polyatomic fragments. This occurs because fewer frequencies are substantially lowered in transition states for the former type of reaction than for the latter. The resulting lower transition state sums of states cause the rates of dissociations producing atoms as fragments to increase much more slowly than competing processes with increasing energy. Here we show that this is why CH3CH3+* formation competes with H* loss from CH3CH2CHO+*. These results further establish that the dependence on energy of the rate of a simple unimolecular dissociation is usually directly related to the number of rotational degrees of freedom in the products, a newly recognized factor in determining the dependence of unimolecular reaction rates on internal energy.