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1.
利用密度泛涵理论对具有四元环、五元环、六元环、七元环、八元环和九元环等的C60富勒烯及其非经典衍生物:C62,C60,C59和C58共8个笼状分子进行了结构优化和电子结构计算,得到平衡构型下的结合能、HOMO-LUMO能隙、电离能、电子亲和能.对具有缺陷环的富勒烯,还研究了H2分子的贯穿行为,讨论了贯穿势垒与缺陷环尺寸的关系.  相似文献   

2.
N-(4-硝基苯基)马来酰亚胺是一种新合成的NPMI类化合物,在B3LYP/6-311++G~(**)水平对N-(4-硝基苯基)马来酰亚胺分子进行几何结构优化和频率、热力学性质计算,得到它的红外光谱、拉曼光谱和不同温度下的热力学性质.结果显示,该分子中两个C=O与五元环在同一个平面内,苯环上硝基中的N—O与六元环也在同一个平面内,五元环与六元环呈129.6°的二面角,整个分子不具有对称性;热容、熵、焓等热力学性质与温度之间存在很好的函数关系式.  相似文献   

3.
首次获得了环戊酮分子8a1轨道的电子动量谱的实验结果,并且给出了价轨道的电离能谱信息.实验用非共面对称几何条件下的能量多道型电子动量谱仪完成,入射电子的能量为1200 eV和600 eV加结合能.Hatree-Fock方法和密度泛函理论计算得到的结果与实验结果作了比较,实验结果和理论计算符合较好.  相似文献   

4.
本文合成了53个多取代的氮苄叉苯胺化合物(XBAY),并测定了它们的核磁共振碳谱和氢谱.包括文献己报导的129个二取代的氮苄叉苯胺化合物分子桥键(CH=N)的碳谱(δ_C(CH=N))和氢谱数据(δ_H(CH=N)),本文研究了共182个取代的XBAY中各取代基对其δ_C(CH=N)和δ_H(CH=N)的影响,分别提出了化合物XB AY分子δ_C (CH=N)和δ_H(CH=N)与取代基参数之间的定量回归方程,该方程可以用来预测取代XB AY的δ_C (CH=N)和δ_H(CH=N)数据,研究结果表明:取代基交叉相互作用项(△(∑σ)~2)对该类化合物的δ_C(CH=N)具有比较大的影响,而对其δ_H(CH=N)的影响基本可以忽略;总体而言,取代基X和Y对化合物XBAY分子δ_C(CH=N)的影响比较均衡,而化合物XBAY分子的δ_H(CH=N)则主要受控于取代基X的影响.  相似文献   

5.
用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理.对三种不同的钐的SS试剂CH3SmCH2X(其中X=Cl、Br和I)分别和CH2CH2反应的各反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证.结果表明:CH3SmCH2X(其中X=Cl、Br和I)与CH2CH2环丙烷化反应按亚甲基转移通道(通道A)和卡宾金属化通道(通道B)都可以进行,与锂类卡宾的反应机理相同,只是按亚甲基转移通道(通道A)进行反应较容易一些,而且此反应在较低的温度下就可以发生.  相似文献   

6.
自由基CH和CH_2的基态结构与势能函数   总被引:1,自引:1,他引:0  
选用OCSD(T)/Aug-cc-PV5Z方法,对CH分子基态的平衡几何进行了优化计算,得到了对应的计算结果.运用含微扰的二次组态相关方法,选用CC-PV5Z基组对CH2分子的基态平衡几何进行了优化计算,得到的结果是:该分子的基态结构为C2v构型,电子态为X3B1,平衡核间距RCH=0.10769nm,键角∠HCH=133.707°,离解能De=5.3277eV,基态振动频率ν1(a1)=1094.24cm-1,ν2(a1)=3144.91cm-1,ν3(b2)=3373.63cm-1.采用多体项展式理论推导了CH2分子基态的解析势能函数,其等值势能图准确再现了CH2分子的结构特征及其势阱深度与位置.在分析讨论势能面的静态特征时,得到了CH H→CH2反应中存在的两个对称鞍点,其活化能为0.13124kJ/mol.  相似文献   

7.
N-(4-硝基苯基)马来酰亚胺是一种新合成的NPMI类化合物,在B3LYP/6-311++G**水平对N-(4-硝基苯基)马来酰亚胺分子进行几何结构优化和频率、热力学性质计算,得到它的红外光谱、拉曼光谱和不同温度下的热力学性质。结果显示,该分子中两个C=O与五元环在同一个平面内,苯环上硝基中的N-O与六元环也在同一个平面内,五元环与六元环呈129.6的二面角,整个分子不具有对称性;热容、熵、焓等热力学性质与温度之间存在很好的函数关系式。  相似文献   

8.
本文首次报道了溴氯甲烷(CH2BrCl)分子在电子入射能为1200 eV 束缚能时价壳层的电离能谱和最高占有轨道的电子动量分布.实验结果与Hartree-Fock(HF)方法和密度泛函理论(DFT)计算进行了比较,表明大基组的密度泛函理论与实验符合较好.  相似文献   

9.
采用含时密度泛函理论,研究了一组线性稠环芳香烃量子点的等离激元激发.沿着线性稠环芳香烃所在的平面方向,体系中有两个主要的等离激元共振带:一个位于3.9 e V附近;另一个位于16 e V附近.随着线性稠环芳香烃长度的增加,在低能共振区,沿不同方向激发时,体系的吸收峰分别发生了蓝移和红移.此外,与并五苯相比,在低能共振区,一氯并五苯的吸收光谱的吸收峰发生了红移和展宽,其中氯原子位于并五苯的两端时对一氯并五苯等离激元激发影响较大.在低能共振区,线性稠环芳香烃的等离激元共振模式与石墨烯量子点相似.  相似文献   

10.
用分子子图法计算硝基呋咱化合物的生成热   总被引:4,自引:0,他引:4       下载免费PDF全文
用新的分子子图法计算硝基呋咱类化合物的生成热 ,将呋咱基团视为母体 ,即基子图项 ;硝基、叠氮基、甲基、氰基拆分为一个个原子 ,从原子的角度来分分子子图 ,将碳、氢、氧、氮原子视为取代基 ,即亚子图项 .同时考虑呋咱基团的个数 ,考虑 1位、2位、3位、4位上碳、氢、氧、氮原子及双键、叁键对生成热的影响 ,还考虑不饱和度、总硝基个数、环的个数 (除呋咱环 )、氮氮及氮氧双键的个数对生成热的影响 .用这种新的分子子图编码方法 ,对硝基呋咱化合物的生成热进行了拟合和预估 ,取得了满意的结果 ,其回归方程的相关系数达到了 0 .995 4 .  相似文献   

11.
采用超声分子束技术,以飞行时间质谱仪,在410~371nm内着重检测了不同波长、不同能量的激光对气相Si(CH3)4分子多光子电离(MPI)飞行时间(TOF)质谱产物分布的影响。根据实验结果,对Si(CH3)4分子多光子解离电离可能经历的通道和反应机理进行了讨论。  相似文献   

12.
We report the first experimental study of ions interacting with clusters of polycyclic aromatic hydrocarbon (PAH) molecules. Collisions between 11.25 keV 3He+ or 360 keV 129Xe20+ and weakly bound clusters of one of the smallest PAH molecules, anthracene, show that C14H10 clusters have much higher tendencies to fragment in ion collisions than other weakly bound clusters. The ionization is dominated by peripheral collisions in which the clusters, very surprisingly, are more strongly heated by Xe20+ collisions than by He+ collisions. The appearance size is k=15 for [C ??H??](k)2+.  相似文献   

13.
Limited configuration interaction Pariser-Parr-Pople calculations were performed for 19 nitrogen heterocyclic aromatic molecules. After optimizing the semiempirical parameters for six “test” molecules, calculations were performed for the remaining thirteen molecules. Strong correlations were made with experimentally observed ionization potentials, singlet-singlet transition energies, polarizations and oscillator strengths as well as ground state molecular geometries for cases where these observations have been made. These correlations indicate spectral features which should be carefully examined experimentally to determine the effect of nitrogen substitution in aromatic hydrocarbon molecules.  相似文献   

14.
A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355?nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones.  相似文献   

15.
We experimentally demonstrate the recognition of positional isomers of propyl alcohol vapor through nonlinear fluorescence induced by high-intensity femtosecond laser filaments in air.By measuring characteristic fluorescence of n-propyl and isopropyl alcohol vapors produced by femtosecond filament excitation,it is found that they show identical spectra,that is,those from molecular bands of CH,C_2,NH,OH and CN,while the relative intensities are different.By comparing the ratios of the CH and C_2 signals,the two propyl alcohol isomers are differentiated.The different signal intensities are ascribed to different ionization potentials of the two isomer molecules,leading to different production efficiencies of fluorescing fragments.  相似文献   

16.
利用飞行时间质谱仪在超声射流冷却条件下探讨了532 nm激光作用下CH3I分子的多光子电离(MPI)解离过程和机制,得到了分子的飞行时间质谱,质谱中包含较强的I 、CH3 离子信号和较弱的CH3I 、CHn (n≤2)、C 、H 离子信号.不同激光能量下的质谱信号在排布上相似,但在强度上有差别.在532 nm激光作用下CH3I分子的多光子电离包括两个过程:一是CH3I分子由双光子激发到A带解离,生成I原子和CH3基团,然后再吸收光子实现中性碎片电离;另一通道是CH3I分子由三光子共振激发到里德堡C态,处于激发态的母体分子继续吸收两个光子电离形成母体离子,碎片离子可由母体离子解离形成.  相似文献   

17.
Ultrafast dissociation dynamics of chloroiodomethane(CH_2ICl)in the B band is studied by femtosecond timeresolved time-of-flight(TOF)mass spectrometry.Time-resolved TOF mass signal of parent ion(CH_2ICl~+)and main daughter ion(CH_2 Cl~+)are obtained.The curve for the transient signal of CH_2ICl~+ is simple and can be well fitted by an exponential decay convoluted with a Gaussian function.The decay constant determined to be less than 35 fs reflects the lifetime of the B band.Significant substituent effects on photodissociation dynamics of CH_2ICl compared with CH3I are discussed.The dissociation time from the parent ion CH_2ICl~+ to the daughter ion CH_2 Cl~+ is determined in the experiment.The optimized geometry of the ionic state of CH_2ICl and the ionization energy are calculated for further analysis of the measurements.In addition,compared with the parent ion,a new decay component with time constant of ~596 fs is observed for CH_2 Cl~+,and reasonable mechanisms are proposed for the explanation.  相似文献   

18.
乙胺分子的多光子电离过程质谱研究   总被引:1,自引:0,他引:1  
报道了乙胺分子在440~475nm波长范围内多光子电离(MPI)质谱(MS)研究结果。碎片离子主要由母体离子碎裂模式产生。母体离子CH3CH2N+·H2由经3s里德堡态的(2+2)共振多光子电离产生后,大部分发生β键断裂,形成CH2=N+H2离子,还有一部分再吸收一个光子,通过C-H(CH2)键的断裂产生了CH3CH=N+H2离子。CH3CH=N+H2和CH2=N+H2离子最容易发生的碎裂过程是脱去氢分子,分别产生C2H4N+(分子式)离子和CH≡N+H离子。  相似文献   

19.
采用蒙特卡罗方法,模拟了CH4/H2混合气体为源气体的EACVD中的氢原子发射过程。考虑了电子与H2的弹性碰撞及振动激发、分解、电子激发、相应于Hα,Hβ,Hγ谱线的激发、电离及分解电离等非弹性碰撞过程;与CH4的碰撞考虑了弹性动量传输及振动激发、分解、电子激发、电离及分解电离等非弹性碰撞过程。研究了不同实验条件下产生的H,CH3的数目与Hδ谱线强度的关系,给出了一种通过Hα谱线来推断生长金刚石薄膜的最佳实验条件的方法。  相似文献   

20.
利用平行板电极装置研究了四甲基硅在410~378 nm内的MPI光谱;利用TOF质谱仪研究了该分子在402~371 nm内若干个波长点处的TOF质谱;利用四极质谱装置研究了它在355 nm处的MPI质谱.测得了355 nm下Si(CH3)+n(n=1,2,3,4)及Si+的激光光强指数,以及其信号强度占总信号强度的分支比随光强的变化关系.据此,讨论了该分子MPI过程的可能通道,得出了Si+主要来自于母体分子的多光子解离-硅原子的电离、Si(CH3)+n(n=1,2,3)主要来自于Si(CH3)n(n=1,2,3)的自电离、Si(CH3)+4来自于母体分子的(3+1)电离的结论.  相似文献   

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