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91.
Ab initio molecular orbital calculations employing a 4-31G basis set have been used to study the minimum energy paths for the formation of HCO+, COH+, and HCOH2+ from CO by protonation. The protonation of N2 to give NNH+ and HNNH2+ and of NO+ to form HNO2+ and NOH2+ have also been investigated. All species formed have linear equilibrium geometries and the minimum energy path for approach of the proton is along the line-of-centers of the heavy atoms. Energy barriers to the formation of the various species are given, where appropriate, and changes in geometry, ordering of molecular orbitals and orbital occupancy are discussed. 相似文献
92.
Preparation of the Iminium Salts CF3? NX?CF2+MF6? (X = CH3, F and M = As, Sb) and CF3? NCl?CF2+ AsF6? The preparation of the iminiumsalts CF3? NX?CF2+ MF6? (X = CH3, F and M = As, Sb) and CF3? NCl?CF2+ AsF6? is reported. The salts were characterized by NMR and infrared spectroscopy. CF3? NCH3?CF2+MF6? decompose into MF5 and (CF3)2NCH3. 相似文献
93.
设计激光投影机光学系统需要从如何减小光学系统的体积和提高激光光源的光效两个方面考虑。研究了激光显示照明系统中的复眼透镜,并对设计的复眼小透镜矩形单元进行了优化,发现在复眼透镜整体尺寸和单颗复眼小透镜焦距一定的情况下,整个复眼透镜上的阵列越多,即复眼透镜上蜂窝的数量越多,其匀光效果就越好,且此时投影机系统的体积也较小。为了提高激光光源的光效,设计中对复眼透镜在不同数值孔径照明光束下的匀光效果进行了讨论。并对优化设计后的复眼透镜进行40 000条光线追迹,实验显示其光线透过率可以达到92.5%,且几乎无杂散光。 相似文献
94.
Dongdong Sun Yong Wu Dr. Xie Han Prof. Simin Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(65):16153-16160
Diarylethene (DTE) has been widely used in fluorescence probes, molecular logic gates, optical data-storage devices owing to the excellent photochromic property, while constructing high-performance photochromic DTE in aqueous media remains a big challenge. Herein we present several host-guest systems formed between cucurbit[n]uril (CB[n], n=7, 8, 10) and two water-soluble DTE derivatives 1 and 2 . It was found that host-guest interactions not only affect the photophysical properties of photochromic guests, but also make great differences on the photoreaction process. Different host-guest binding behaviors also lead to different effects on the photochromic properties of guests. In the presence of CB[n], both 1 and 2 showed enhanced emission and higher fluorescence quenching ratio at photostationary state. Besides, CB[10] ⋅1 exhibited faster response rate in cyclization reaction and better photofatigue resistance than free 1 in aqueous solution, while the supramolecular assembly of (CB[8])n ⋅ ( 2 )n showed slower response rate in both directions of the reversible photoreaction. Besides, the photofatigue resistance of 2 can be greatly improved through binding with CB[7]. Our results suggest that host-guest interactions could be an efficient way to improve photochromic properties of DTE in aqueous solution. 相似文献
95.
ZHANG Cong-jie CAO Ze-xing ** ZHANG Qian-er . State Key Laboratory for Physical Chemistry of Solid Surface Department of Chemistry Center for Theoretical Chemistry Xiamen University Xiamen P. R. China . Department of Chemistry Shanxi Normal University Linfen P. R. China 《高等学校化学研究》2003,(4)
IntroductionCarbon chains are among the most attractivecandidates as the carriers of the diffuse interstellarbands ( DIBs) [1] .To detect the carbon chains indark clouds and carbon stars[2 ] ,itis very importantto understand their electronic spectra.Maier andhis coworkers have measured the polyacetylenicradicals C2 n H( n=1— 4) and C2 n-1H( n=2— 6) bythe rotational spectroscopy[3 ,4] and the species n≤ 4have been detected in dark interstellar clouds[5,6] .In neon matrices,the B2 Π← X2… 相似文献
96.
对甲苯磺酸催化合成乙酸正丁酯 总被引:8,自引:0,他引:8
用对甲苯磺酸作冰乙酸和正丁醇的酯化催化剂,成功地合成了乙酸正丁酯,考察了影响反应的因素,探讨并找到了较好的反应条件:乙酸l00mmol,n(冰乙酸):n(正丁醇):n(催化剂)=1:3:0.006,反应时间1.5h,不另加带水剂,产率达99.14%。 相似文献
97.
用密度泛含方法研究了LaC5n(n=-1,0,+1)分子簇的结构和稳定性及振动光谱,对这个六原子体系提出了三种可能构型,点群结构为C2v对称性.第一个构型为La接在弯曲的C5链上,第二个是La通过二个键与C5环相连第三个是La通过一个键与C5环相连;结果表明,第一个构型即当La接在弯曲的C5链上时能量最低.振动光谱分析指出,当n=-1时,第二个构型为局域极小值;当n=+1时,第一个和第二个构型为局域极小值;对n=0,局域极小值没有找到. 相似文献
98.
采用密度泛函理论(DFT)研究了螺桨烷型分子BX[(CH2)n]3和BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的结构、稳定性、化学键和电子光谱性质.计算结果表明这些分子都是稳定的.BX[(CH2)n]3(X=N,P;n=1-6)的最高占据分子轨道(HOMO)和最低空分子轨道(LUMO)之间的能隙均大于5.20 eV,其中BN[CH2]3和BP[CH2]3的能隙超过7.0 eV,与C5H6的能隙(7.27 eV)很接近,BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的能隙在6.80 eV左右.所研究分子能量的二阶差分表明BN[(CH2)3]3、BP[(CH2)4]3及BX(CH2)[CH(CH2)2CH](X=N,P)是最稳定的.BX[(CH2)n]3的Wiberg键级表明除了BN[(CH2)n]3(n=2和6)中不存在B―N键,其它化合物中B和N均形成了化学键,BP[(CH2)n]3中除了BP[(CH2)2]3不存在B―P键,其它的均存在.电子密度的拓扑分析表明N―B键属于离子键,而P―B键具有共价键特征.BX[(CH2)n]3(X=N,P)的第一垂直激发能分别在191.1-284.8 nm和191.8-270.1 nm之间,BX(CH2)[CH(CH2)n CH](X=N,P)的第一垂直激发能分别在190.5-199.7 nm和209.0-221.3 nm之间. 相似文献
99.
C. Y. Zhu R. M. Izatt J. S. Bradshaw N. K. Dalley 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(1):17-27
Equilibrium constant (K), enthalpy change (H), and entropy change (S) values have been determined calorimetrically at 25°C in 90%MeOH 10%H2O (v/v) for the interactions of pyridino-18-crown-6 (P18C6) and diketopyridino-18-crown-6 (K2P18C6) with perchlorate salts of ammonium, benzylammonium,-phenylethylammonium,-phenylethylammonium, and-(1-naphthyl)ethyl-ammonium cations. The crystal structure of the complex of P18C6 with benzylammonium perchlorate was determined by X-ray crystallography. The1H 1D and 2D NMR spectra of some of these complexes were used to elucidate their structural features in solution. The logK values for the interaction of the ammonium cations with P18C6 are larger than those with K2P18C6, probably due to the higher degree of structural flexibility of P18C6. Ligand K2P18C6 displays appreciable - interaction with the-(1-naphthyl)ethylammonium cation, but not with the-phenylethylammonium cation.- interaction between ligand and cationSupplementary Data relating to this article are deposited with the British Library as Supplementary Publication No SUP 00000 (22 pages) 相似文献
100.