共查询到20条相似文献,搜索用时 78 毫秒
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对γ-氨丙基杂氮硅三环,γ-乙二胺基丙基杂的氮硅三环,γ-乙二撑三胺基丙基杂质硅三环3种化合物的红外光谱进行了研究,胺基的特征吸收为:伸缩振动υas(NH)和υs(NH);剪式振动δ(NH2)。三环的特征吸收为:CH2的弯曲振动ω(CH2N)ω(CH2O)和τ(CH2O);C-O键的伸缩振动υ(C-O);N-C键的伸缩振动υ(NC3)和υ(NC3),Si-O键的伸缩振动υ(Si-O)和υ(Si-O 相似文献
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本文对二十四个氮杂硅三环类化合物进行了质谱研究.测定了它们的低分辨质谱,收集了大部分化合物的高分辨质谱数据并进行了亚稳跃迁测定。结果表明,分子离子的稳定性、基峰的生成方式以及碎片离子的多少主要取决于取代基R的性质.分子的电子轰击质谱裂解存在三种基本方式:(1)断裂Si~R键,生成高度稳定的(M-R)~ 离子,碎片离子较少;(2)开环,失去碎片C_2H_3O;(3)开环,失去碎片CH_2O或CH_3O.用电荷自由基定域理论解释这类化合物的质谱裂解机理,并对影响分子离子稳定性的有关因素及影响基峰形成的原因进行了讨论. 相似文献
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杂氮硅三环是一类分子内具有N→Si配位键的化合物,作者曾报道了一系列该类化合物的合成方法和化学结构。对于一个分子内带两个对称的硅三环结构的双一杂氮硅三环化合物的合成,文献报道还很少啪。我们用下 相似文献
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对γ-氨丙基杂氮硅三环、γ-乙二胺基丙基杂氮硅三环、γ-乙二撑三胺基丙基杂氮硅三环3种化合物的红外光谱进行了研究。胺基的特征吸收为:伸缩振动v_(as)(NH)和v_s(NH);剪式振动δ(NH_2)。三环的特征吸收为:CH_2的弯曲振动ω(CH_2N)、ω(CH_2O)和τ(CH_2O);C-O键的伸缩振动v(C-O);N-C键的伸缩振动v_(as)(NC_3)和v_s(NC_3);Si-O键的伸缩振动v_(as)(Si-O)和v_s(Si-O);C-C键的伸缩振动v(C-C);以及Si←N配键的伸缩振动v(Si←N)。 相似文献
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γ—芳亚甲氨基丙基杂氮硅三环的合成及其抗肿瘤活性研究 总被引:4,自引:0,他引:4
γ-氨基丙基杂氮硅三环与一系列芳香醛反应,合成了14种γ-芳亚甲氨基丙基杂氮硅三环化合物。用~1H NMR、IR、UV和元素分析确定了它们的化学结构。初步动物实验表明,某些化合物具有一定的抗肿瘤活性。 相似文献
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报道了10种杂氮硅三环类化合物的紫外光电子能谱(UPS).采用RHF/3-21G*对各化合物进行了构型优化.根据各化合物UPS的谱带特征结合RHF/6-31G*的计算结果对谱图进行了合理的解析和指认.利用6-31G*基组进行的电子密度拓扑分析表明,各化合物的N和Si原子间均存在键鞍点,从理论上证实了N和Si原子间存在成键作用.各化合物的UPS和SCFMO计算和电子密度拓扑分析都表明,在该类体系中σN→Si配键是比杂氮硼三环类化合物中σN→B配键弱得多的成键作用;文中同时讨论了不同取代基对Si和N间成键作用的影响. 相似文献
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Victor García David Zorrilla Manuel Fernández 《International journal of quantum chemistry》2014,114(23):1581-1593
We introduce a new type of spatially restricted basis function (zero beyond a characteristic r0 value of the radial coordinate) that makes it possible to obtain, in nonconfined systems, similar results to STO functions. This is important because the use of this kind of functions enables the exact application a sort of zero differential overlap approximation to calculate properties of large systems. Our functions are a modification of the BO‐xZ box orbitals introduced by Lepetit et al. First, we replaced these orbitals by a function that is easier to obtain and generalize, that we named “simplified box orbital” (SBO), and we have shown some advantages of the SBO over BO and standard STO functions. Second, we obtained Gaussian developments for both the original BO orbitals and the new SBO orbitals. In this way, it becomes possible to manage our SBO orbitals with standard quantum chemistry software like GAUSSIAN or similar programs. © 2014 Wiley Periodicals, Inc. 相似文献
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A technique to reduce the computational effort in calculating ab initio energies using a localized orbitals approach is presented. By exploiting freeze strategy at the self-consistent field (SCF) level and a cut of the unneeded atomic orbitals, it is possible to perform a localized complete active space (CAS-SCF) calculation on a reduced system. This will open the possibility to perform ab initio treatments on very large molecular systems, provided that the chemically important phenomena happen in a localized zone of the molecule. Two test cases are discussed, to illustrate the performance of the method: the cis-trans interconversion curves for the (7Z)-13 ammoniotridec-7-enoate, which demonstrates the ability of the method to reproduce the interactions between charged groups; and the cisoid-transoid energy barrier for the aldehydic group in the C13 polyenal molecule. 相似文献
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An efficient algorithm for energy gradients in valence bond theory with nonorthogonal orbitals is presented. A general Hartree-Fock-like expression for the Hamiltonian matrix element between valence bond (VB) determinants is derived by introducing a transition density matrix. Analytical expressions for the energy gradients with respect to the orbital coefficients are obtained explicitly, whose scaling for computational cost is m(4), where m is the number of basis functions, and is thus approximately the same as in HF method. Compared with other existing approaches, the present algorithm has lower scaling, and thus is much more efficient. Furthermore, the expression for the energy gradient with respect to the nuclear coordinates is also presented, and it provides an effective algorithm for the geometry optimization and the evaluation of various molecular properties in VB theory. Test applications show that our new algorithm runs faster than other methods. 相似文献
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本文用量子化学从头算方法研究了甲烷与配位不饱和PtCl2(H2O)x(x=0,1,2)形成的σ配合物的结构和性质。通过RHF/Lan12DZ和MP2/Lan12DZ水平计算讨论了溶剂H2O分子与位的影响。在RHF/Lan12DZ级别上有4个稳定的(CH4)PtCl2配合物,分别属于η^3,η^2,η^3,并都具有Cs对称性。根据能量和结构分析,η^1配合物是进一步氧化加成反应的可能的起始物。 相似文献
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ATheoreticalStudyontheHydrogen-bondedDimersofHNCOMoleculesWangYan;FengWen-Lin;ZhangShao-Wen;ZhuWei-Xin(ChemistryDepartment,Be... 相似文献
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《International journal of quantum chemistry》2018,118(3)
The existence and gas phase stability of silicon analogues of three natural amino acids (i.e., silicon glycine, silicon alanine, and silicon valine) belonging to the novel class of compounds termed silicon amino acids (SiAA) are investigated theoretically on the basis of ab initio QCISD/aug‐cc‐pVTZ and MP2/aug‐cc‐pVTZ calculations. All molecules studied (in their gas phase canonical forms) are structurally comparable to their proteinogenic counterparts (i.e., glycine, l ‐alanine, and l ‐valine) and capable of forming several structural isomers as such. These higher energy isomers are characterized by small relative energies (not exceeding 4 kcal mol−1). The simulated IR spectra of the Si‐Gly, Si‐Ala, and Si‐Val global minima are also presented and discussed. 相似文献