共查询到17条相似文献,搜索用时 125 毫秒
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应用密度泛函理论,在B3LYP/6-31G水平上优化了线性簇合物SC2nS2-(n=1~12)的基态平衡几何结构,并计算了它们的谐振动频率.在基态平衡构型下,通过TD-B3LYP/cc-pvTZ和TD-B3LYP/cc-pvDZ计算,确定了簇合物SC2nS2-(n=1~10)X1Σ g→11Σ u电子跃迁的垂直激发能和对应的振子强度.基于计算结果,导出了X1Σ g→11Σ u电子跃迁吸收波长与体系大小n的解析关系式,以及SC2nS2-体系第一电离能与体系大小n的解析表达式,并讨论了不同端位原子对碳链体系激发态性质的影响. 相似文献
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二(对甲基苄基)二氯化锡和氢氧化钠溶液反应,合成了梯形结构二(对甲基苄基)锡氧(氯)簇合物,经X-射线衍射测定了其晶体结构。属三斜晶系,空间群为P1,晶体学参数a=0.979 52(16) nm,b=1.313 8(2) nm,c=1.419 5(2) nm,α=62.965(10)°,β=88.551(12)°,γ=73.709(11)°,V=1.550 5(5) nm3,Z=1,Dc=1.563 g·cm-3,μ(Mo Kα)=17.38 cm-1,F(000)=727,R=0.024 2,wR=0.057 9。簇合物为由Sn2O2构成的平面四元环形成的1个中心内环和2个由Sn2OCl(O)构成的平面四元外环组成的梯形结构。锡原子均为五配位三角双锥构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。 相似文献
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Si_2C_(m-2)(m=4~15)团簇的结构与稳定性 总被引:1,自引:0,他引:1
用密度泛函理论(DFT)的B3LYP/6-31G*方法, 对Si2Cm-2(m = 4~15)团簇的几何构型、电子结构、振动频率等性质进行了研究, 讨论了化学键的特征和热力学稳定性, 比较了Si2Cm-2团中环状和线状结构的差异。结果表明, m = 4~13的团簇为线状结构, m=14~15的团簇为环状结构。在线状结构中, 随着m增大, 自旋多重度出现1、3交替变化, 并且Si原子倾向于在C链端部成键;环状结构中, C原子形成环状, 2个Si原子处于椭圆环状构型的两端。m 为奇数的Si2Cm-2团簇比m为偶数的更为稳定。 相似文献
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Structures,Energetics, and Infrared Spectra of the Cationic Monomethylamine-Water Clusters 下载免费PDF全文
Shu-kang Jiang Dong Yang Xiang-tao Kong Chong Wang Xiang-yu Zang Hui-jun Zheng Gang Li Hua Xie Wei-qing Zhang Xue-ming Yang Ling Jiang 《化学物理学报(中文版)》2020,33(1):31-36
The structures, energetics, and infrared (IR) spectra of the cationic monomethylamine-water clusters, [(CH\begin{document}$_3$\end{document} NH\begin{document}$_2$\end{document} )(H\begin{document}$_2$\end{document} O)\begin{document}$_n$\end{document} ]\begin{document}$^+$\end{document} (\begin{document}$n$\end{document} =1\begin{document}$-$\end{document} 5), have been studied using quantum chemical calculations at the MP2/6-311+G(2d,p) level. The results reveal that the formation of proton-transferred CH\begin{document}$_2$\end{document} NH\begin{document}$_3$\end{document} \begin{document}$^+$\end{document} ion core structure is preferred via the intramolecular proton transfer from the methyl group to the nitrogen atom and the water molecules act as the acceptor for the O\begin{document}$\cdots$\end{document} HN hydrogen bonds with the positively charged NH\begin{document}$_3$\end{document} \begin{document}$^+$\end{document} moiety of CH\begin{document}$_2$\end{document} NH\begin{document}$_3$\end{document} \begin{document}$^+$\end{document} , whose motif is retained in the larger clusters. The CH\begin{document}$_3$\end{document} NH\begin{document}$_2$\end{document} \begin{document}$^+$\end{document} ion core structure is predicted to be less energetically favorable. Vibrational frequencies of CH stretches, hydrogen-bonded and free NH stretches, and hydrogen-bonded OH stretches in the calculated IR spectra of the CH\begin{document}$_2$\end{document} NH\begin{document}$_3$\end{document} \begin{document}$^+$\end{document} and CH\begin{document}$_3$\end{document} NH\begin{document}$_2$\end{document} \begin{document}$^+$\end{document} type structures are different from each other, which would afford the sensitive probes for fundamental understanding of hydrogen bonding networks generated from the radiation-induced chemical processes in the [(CH\begin{document}$_3$\end{document} NH\begin{document}$_2$\end{document} )(H\begin{document}$_2$\end{document} O)\begin{document}$_n$\end{document} ]\begin{document}$^+$\end{document} complexes. 相似文献
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选择3种不同尺寸含氮配体(哌嗪、咪唑和三氮唑)与三羟甲基丙烷(H3tmp)和FeCl3采用溶剂热反应合成3例六核Fe(Ⅲ)合物:(C5H14N2)[Fe6(μ6-O)Cl6(tmp)4]·2H2O·CH3OH (1)、(C3H5N2)2[Fe6(μ6-O)Cl6(tmp)4] (2)和(C4H8N3)3(C2H4N3)[Fe12(μ6-O)2Cl12(tmp)8]·3CH3OH (3),并对它们的结构进行表征。发现三元醇配体有利于合成高核金属簇。3个化合物具有相同的阴离子簇[Fe6(μ6-O)Cl6(tmp)4]2-。通过晶体学参数,元素分析,红外等手段证实,在化合物1和3的体系中,氮杂环配体经历了N-和C-烷基化反应。 相似文献
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用 HF自洽场理论和密度泛函理论 (DFT)的 B3LYP方法 ,在 6 31G水平上研究了低聚物 (Cl2AlNH2)n和 (H2AlNH2)n(n=1~ 5)簇的几何构型、电子结构和聚合反应热力学性质 ,比较了两个系列化合物中化学键的强度 .结果表明 ,Cl2AlNH2和 H2AlNH2分子为 C2υ (EC)平面型结构 ,其中 Al- N为由一个σ键和一个π键组成的双键 .(Cl2AlNH2)n和 (H2AlNH2)n(n=1~ 5)分子为 Dnh对称 ,Al- N是典型的σ单键 .低聚物 (Cl2AlNH2)n和 (H2AlNH2)n的稳定性顺序分别为 : 3 > 2 > 4> 5 > 1和 8 > 7 > 9 > 11 > 6. 相似文献
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Li Hua He Jing Lin Chen Jin Yun Wang Xiu Xiu Chen Xiu Zhen Tan Xing Fu Cao 《中国化学快报》2012,23(10):1169-1172
Two new copper(I) halide complexes bearing 2-(2-benzimidazolyl)-6-methylpyridine(Hbmp) and PPh3 ligands, Cu(Hbmp)(PPh3)X(X = Br(1);I(2)),have been synthesized and characterized.Single-crystal X-ray structure analysis reveals that the halide ligand has a significant impact on the Cu-Npyridyl bond lengths.Complexes 1 and 2 show the solid-state emissions at ambient temperature,varying with the halide bound to the {Cu(Hbmp)(PPh3)} motif,which are perhaps best attributed to the metal-to-ligand charge-transfer(Cu(I)→Hbmp) transition mixed with some ligand-to-ligand charge-transfer(X and PPh3→Hbmp) character. 相似文献
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用1,3-双(2-甲酰基苯氧基)-2-丙醇和丙二腈进行反应得到1,3-双(2-(2,2-二氰乙烯基)苯氧基)-2-丙醇配体L,然后将配体与Ag Sb F6进行配位反应,得到配合物[Ag LSb F6]n·n CHCl3(1),并用元素分析,FTIR和X-射线单晶衍射进行了表征。结果表明,配体L属于单斜晶系,空间群P21/n,晶体学参数:a=0.990 2(11)nm,b=2.181(2)nm,c=1.012 2(11)nm,β=109.374(10)°,V=2.062(4)nm3,Z=4,Dc=1.277 g·cm-3,Mr=396.40,μ=0.087 mm-1,F(000)=824,R1=0.064 2,w R2=0.117 4(I>2σ(I))。配合物1属于单斜晶系,空间群P21/n,晶体学参数:a=1.270 57(11)nm,b=1.456 44(13)nm,c=1.669 85(14)nm,β=105.643(3)°,V=2.975 6(4)nm 3,Z=4,Dc=1.918 g·cm-3,Mr=859.39,μ=1.907 mm-1,F(000)=1 664,R1=0.0417,w R2=0.1 032(I>2σ(I))。在配合物1中,配体L表现为四齿配体分别与4个银(Ⅰ)离子配位,同时,每一个银(Ⅰ)离子与4个相邻配体配位形成2D层状结构。同时,研究了配体和配合物的固体荧光性质。 相似文献
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1 INTRODUCTION The chemistry of organotin(IV) complexes was extensively studied due to their biological activity and coordination chemistry[1~7]. More recently, phar- maceutical properties of alkyltin(IV) complexes with dithiocarbamate ligands have bee… 相似文献
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Wen-Shu Hwang Chung-Jeh Hwang Dong-Liang Wang Liang-Shiu Lee Michael Y. Chiang 《中国化学会会志》1998,45(4):555-561
N,N′-1,2-phenylenebis(2-thienylideneimine) (PTI) can be obtained via the condensation of o-phenylenediamine and thiophene-2-carboxaldhyde in cyclohexane. It isomerized to its cyclic form 1-(2-thienylmethyl)-2-(2-thienyl)benzimidazole (TMTBI) readily in the presence of Fe2(CO)9. Coordination reactions of PTI with cuprous iodide and silver nitrate in acetonitrile resulted in the formation of [Cu(TMTBI)I]2 and [Ag(TMTBI)2]NO3, respectively, in which the PTI ligand had been isomerized to TMTBI. Both PTI, TMTBI, and complexes were characterized by NMR, IR, and Mass spectroscopies as well as elemental analysis. The crystal structures of TMTBI and [Cu(TMTBI)I]2 were determined by single-crystal X-ray diffraction. Crystallographic details for X-ray structures are as follows. TMTBI is crystallized in the monoclinic space group P21/n with a = 8.953(3), b = 9.150(1), c = 17.436(2) Å, β = 93.73(2)°, and Z = 4. The final R factor was 0.050 (Rw = 0.066) for 1337 observed reflections. Complex [Cu(TMTBI)I]2 is crystallized in the triclinic space group $ {\rm P}\bar 1 $ with a = 9.961 (2), b = 10.825(2), c = 9.184(2) Å, α = 112.98(2), β = 110.78(2), γ = 88.71 (2)°, and Z = 2. The final R factor was 0.056 (Rw = 0.057) for 2363 observed reflections. 相似文献