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A new Λ type pyriding iodide was synthesized by reaction of 4-picoline and methyl diiodide. The structure was characterized by elemental analysis, IR, UV and TG. The crystal structure of the title compound was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic with space group C2/c, a=18.812(4)?, b=8.7816(6)?, c=10.3165(12)?, β=93.71(1), V=1700.7(4)?3, Z=4. In the molecule, two 4-picoline molecules are bonded by -CH2 group to form Λ type pyridine salt. CCDC: 180871. 相似文献
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Π态双原子分子Λ分裂引起的量子干涉 总被引:1,自引:0,他引:1
To interpret theoretically the abnormal phenomenon in the experiment of collision-induced rotational energy transfer of CO(A1Π,v=3)with He by Sun et al.,the time dependent first order Born approximation,and the long-range interaction potentials and“straight-line”trajectory approximation are taken into account. A theoretical model of quantum interference of Π-state diatomic molecules,which originates from the difference between the two "Λ-related collision potential energy surface,is presented. The abnormal phenomenon of σε→ε'ΔJ=0<σε→ε'ΔJ=±1 for He is also interpreted successfully. At first the theoretical development of collision-induced quantum interference on rotational energy transfer is reported;then a theoretical model of quantum interference of Π-state diatomic molecules,which originates from the difference between the two "Λ-related collision potential energy surfaces,is presented;in the end the results have been discussed and concluded. 相似文献
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Alfred Schmidpeter Jörg Luber Helmut Riedl Manfred Volz 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):171-174
Abstract Die Kondensation von N 1-substituierten N-Acetyl-und-Benzoyl-hydrazinen mit P[N(CH3)2]3 oder CH3P[NCH3)2]2 fuhrt stets zu 3-substituierten 1.3.4.2Λ3-Oxadizaphospholinen, auch wenn der jeweilige Substituent die Bildung von anderen isomeren Fünfringen oder von Isomeren mit größerem Ring oder eine weitergehende Kondensation zuließe. Sie können in die 2.2-Dichloro- und 2-Thioxo-1.3.4.2Λ5-Oxadiazaphospholine übergeführt werden. Condensation of N 1-substituted N-acetyl and N-benzoyl hydrazines with P[N(CH3)2]3 or CH3P[N(CH3)2] 2 always gives 3-substituted 1.3.4.2Λ3-oxadiazaphospholines, even if the substituent would allow other isomeric five membered or larger ring phosphorus heterocycles to be formed, or the condensation to proceed further. The title compounds can be oxidized to 2.2-dichloro and 2-thioxo 1.3.4.2Λ5-oxadiazaphospholines. 相似文献
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在由G矩阵因解和频率确定力常数的计算中,找到了适用于任意维A矩阵相对于L矩阵按对称坐标排列顺序的关系;用逆酉变换得到了由复合力常数F_s计算F_R的一般方法;确立了F_R按对称块的加和性。以尿素等分子为例,用一般价力场计算了全部力常数F_R,频率计算值(低频部分)更符合实验结果。 相似文献
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本文选择Λ-型TB骨架作为分子的基本框架, 将二腈基异弗乐酮引入其中, 采用简便方法合成了一种具有聚集态荧光增强现象的红光材料2,8-双[2-(5,5-二甲基-环乙烯基-2-烯基)丙二腈]-6H,12H-5,11-甲基二苯[b,f][1,5]二氮芳辛(DMCEM). 同时, 制备了粒径不同的DMCEM纳米颗粒, 并对其光学性质进行了研究. 相似文献
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Donakowski MD Gautier R Yeon J Moore DT Nino JC Halasyamani PS Poeppelmeier KR 《Journal of the American Chemical Society》2012,134(18):7679-7689
A methodology for the design of polar, inorganic structures is demonstrated here with the packing of lambda (Λ)-shaped basic building units (BBUs). Noncentrosymmetric (NCS) solids with interesting physical properties can be created with BBUs that lack an inversion center and are likely to pack into a polar configuration; previous methods to construct these solids have used NCS octahedra as BBUs. Using this methodology to synthesize NCS solids, one must increase the coordination of the NCS octahedra with maintenance of the noncentrosymmetry of the bulk. The first step in this progression from an NCS octahedron to an inorganic NCS solid is the formation of a bimetallic BBU. This step is exemplified with the compound CuVOF(4)(H(2)O)(7): this compound, presented here, crystallizes in an NCS structure with ordered, isolated [Cu(H(2)O)(5)](2+) cations and [VOF(4)(H(2)O)](2-) anions into Λ-shaped, bimetallic BBUs to form CuVOF(4)(H(2)O)(6)·H(2)O, owing to the Jahn-Teller distortion of Cu(2+). Conversely, the centrosymmetric heterotypes with the same formula MVOF(4)(H(2)O)(7) (M(II) = Co, Ni, and Zn) exhibit ordered, isolated [VOF(4)(H(2)O)](2-) and [M(H(2)O)(6)](2+) ionic species in a hydrogen bond network. CuVOF(4)(H(2)O)(7) exhibits a net polar moment while the heterotypes do not; this demonstrates that Λ-shaped BBUs give a greater probability for and, in this case, lead to NCS structures. 相似文献
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六元碳环邻位对称取代的Λ-型分子非线性光学系数的计算 总被引:1,自引:1,他引:0
采用密度泛函理论(DFT)的BHandHLYP/6-31G*方法,对3类含有六元碳环的Λ-型分子的几何构型进行优化.在优化结构的基础上,结合有限场方法(FF)和含时密度泛函理论(TD-DFT)对分子的二阶非线性光学(NLO)活性及电子吸收光谱进行研究.结果表明,在拐点处环己烷的构象不同时,分子电荷分布、偶极矩、极化率、二阶NLO系数和电子吸收光谱等变化很小.以苯环为拐点片段的分子有所不同,当支链取代基R增大时,以苯环为拐点片段分子的极化率和二阶NLO系数增加明显. 相似文献
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Sha等在静态池实验中观察到了转动能量转移中的碰撞量子干涉,并且计算了决定跃迁散射截面的积分干涉角(J.Chem.Phys.,1995,102:2772).由于积分干涉角是微分干涉角的平均效应,为了得到更精确的信息,进行了分子束实验.作者文运用含时微扰的一级波恩近似理论,提出了衡量干涉程度的1П态双原子分子中关于Λ量子干涉的微分干涉角.利用各向异性相互作用势计算了其干涉角.得到分子束实验中微分干涉角随实验参数,包括实验温度、碰撞伴、作用距离和转动量子数变化的关系.并且讨论了影响干涉角的各种参数.此理论模型对理解和进行分子束实验是非常重要的. 相似文献
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Rachel L. BeingessnerJulian A. Diaz Usha D. HemrazHicham Fenniri 《Tetrahedron letters》2011,52(6):661-664
Progress toward the synthesis of guanine-cytosine (GΛC) oligonucleotides for the spontaneous self-assembly of rosette nanotubes (RNTs) with predefined length is described. Highlighted is the synthesis of the β-glycoside functionalized GΛC base along with a new nitrogen protecting group strategy that is compatible with Boc and Bn groups. 相似文献
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针对国际上对金属配合物同DNA间作用机量的争议,采用分子模拟手段在MM2力场下,搭建并优化了手性金属配合物△,Λ-[Co(phen)2tpphz]^3+与B-DNA[d(GTCGATCGAC)2]的模型,继而对其相互作用进行了模拟,得出的结论是:对所采用的B-DNA片断,该金属配合物有明显的立体选择性△型配合物从小沟插入占明显优势,而且,总体来看,从AT区插入更易进行。 相似文献
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针对国际上对金属配合物同DNA间作用机量的争议,采用分子模拟手段在MM2力场下,搭建并优化了手性金属配合物△,Λ-[Co(phen)2tpphz]^3+与B-DNA[d(GTCGATCGAC)2]的模型,继而对其相互作用进行了模拟,得出的结论是:对所采用的B-DNA片断,该金属配合物有明显的立体选择性△型配合物从小沟插入占明显优势,而且,总体来看,从AT区插入更易进行。 相似文献
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本文通过在ESFF(Extensible Systematic Force Field)力场下对其作用中的体系势能进行分子力学计算,分析了手性金属配合物Λ-及Δ-[Ru(phen)2dppz]^n 对错配DNA d(CCGAATGAGG)2的识别机理,并在分子水平上对其做了详细解释。 相似文献
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利用分子模拟方法, 通过研究手性金属配合物[Co(phen)2dppz]3 (phen = 1, 10-phenanthroline, dppz = dipyrido[3, 2-a: 2′, 3′-c]phenazine)与B-DNA的作用机理, 探讨了当前存在争议的两种模型: 即Barton的从DNA大沟插入、且 D 型异构体更易于和B-DNA结合的模型和Norden的从DNA小沟插入、且没有显著异构体选择性的模型.最终, 研究结果支持Norden的结合模型, 而对Barton的结合模型提出了异议. 相似文献
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通过分子模拟方法研究了手性金属配合物[Rh(bpy)2Chrysi]3 (bpy=2,2’- bipyridine;Chrysi=5,6-chrysenequinonediimine)对包含C:T错配碱基对的B-DNA序列的识别作用。结合类似的针对含G:A错配的和正常的B-DNA序列的识别作用研究,发现配合物[Rh(bpy)2Chrysi]3 可以对错配B-DNA序列进行序列特异性的识别.能量对比计算结果表明,该经典插入识别作用倾向于在错配碱基对附近进行,其中Δ-[Rh(bpy)2charysi]3 比其手性异构体更占优势.这同Barton教授工作组的实验结果是一致的。另外插入作用倾向于在错配序列中的正常双碱基对C3A4/G374(错配碱基对附近)中从小沟进行.与该配合物对含G:A错配的和正常的B-DNA序列的识别作用不同的是,对包含C:T错配碱基对的B-DNA序列的识别作用倾向于从小沟进行.这一点可能源于C:T碱基对结构的不同. 相似文献
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Symmetric and asymmetric triple excitation corrections for the orbital-optimized coupled-cluster doubles (OO-CCD or simply "OD" for short) method are investigated. The conventional symmetric and asymmetric perturbative triples corrections [(T) and (T)(Λ)] are implemented, the latter one for the first time. Additionally, two new triples corrections, denoted as OD(Λ) and OD(Λ)(T), are introduced. We applied the new methods to potential energy surfaces of the BH, HF, C(2), N(2), and CH(4) molecules, and compare the errors in total energies, with respect to full configuration interaction, with those from the standard coupled-cluster singles and doubles (CCSD), with perturbative triples [CCSD(T)], and asymmetric triples correction (CCSD(T)(Λ)) methods. The CCSD(T) method fails badly at stretched geometries, the corresponding nonparallelity error is 7-281 kcal mol(-1), although it gives reliable results near equilibrium geometries. The new symmetric triples correction, CCSD(Λ), noticeably improves upon CCSD(T) (by 4-14 kcal mol(-1)) for BH, HF, and CH(4); however, its performance is worse than CCSD(T) (by 1.6-4.2 kcal mol(-1)) for C(2) and N(2). The asymmetric triples corrections, CCSD(T)(Λ) and CCSD(Λ)(T), perform remarkably better than CCSD(T) (by 5-18 kcal mol(-1)) for the BH, HF, and CH(4) molecules, while for C(2) and N(2) their results are similar to those of CCSD(T). Although the performance of CCSD and OD is similar, the situation is significantly different in the case of triples corrections, especially at stretched geometries. The OD(T) method improves upon CCSD(T) by 1-279 kcal mol(-1). The new symmetric triples correction, OD(Λ), enhances the OD(T) results (by 0.01-2.0 kcal mol(-1)) for BH, HF, and CH(4); however, its performance is worse than OD(T) (by 1.9-2.3 kcal mol(-1)) for C(2) and N(2). The asymmetric triples corrections, OD(T)(Λ) and OD(Λ)(T), perform better than OD(T) (by 2.0-6.2 kcal mol(-1)). The latter method is slightly better for the BH, HF, and CH(4) molecules. However, for C(2) and N(2) the new results are similar to those of OD(T). For the BH, HF, and CH(4) molecules, OD(Λ)(T) provides the best potential energy curves among the considered methods, while for C(2) and N(2) the OD(T) method prevails. Hence, for single-bond breaking the OD(Λ)(T) method appears to be superior, whereas for multiple-bond breaking the OD(T) method is better. 相似文献
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Δ-和Λ-[Ru(bpy)2(HPIP)2+两种异构体对小牛胸腺DNA不同键合速率的CD光谱证明 总被引:2,自引:0,他引:2
Wilson[1]于1997年发表了关于DNA导电性的评论性文章, 介绍了各种学派的观点. 争论焦点在于DNA是否为导体. 将两种配合物键合于DNA作为接头, 通过研究电子转移可确定DNA是否为导线, 其中配合物和DNA键合模式是研究的关键. Barton[2]和Norden[3]均认为2+ 配合物能强烈插入DNA中. 我们[4]曾从改变辅助配体角度出发, 研究2+和DNA的作用, 结果证明2+具有更强的插入能力, 并结合文献把键合模式归纳为3类, 即静电键合、沟面键合和插入键合[5]. 最近, 我们报道了新体系2+/DNA/2+(bpy=2,2′-bipyridine), 其中2+和2+均可插入DNA中. 2+是光诱导电子给予体, 2+是电子接受体, 荧光光谱证明前者的电子通过DNA中的π电子转移给后者, 导致后者荧光猝灭, 结果支持DNA是导线的观点[6]. 2+中的PIP芳香环和DNA碱基芳环组成π电子的堆积力[7], 从而增强了对DNA的插入能力. 相似文献
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通过分子模拟方法研究了手性金属配合物[Rh(bpy)2Chrysi]^3+(bpy=2,2’-bipyridineChrysi=5,6-chrysenequinonediimine)对包含C:T错配碱基对的B-DNA序列的识别作用.结合类似的针对含G:A错配的和正常的B-DNA序列的识别作用研究,发现配合物I-Rh(bpy)zChrysi]^3+可以对错配B-DNA序列进行序列特异性的识别.能量对比计算结果表明,该经典插入识别作用倾向于在错配碱基对附近进行,其中△-[Rh(bpy)2chrysi]^3+比其手性异构体更占优势.这同Barton教授工作组的实验结果是一致的.另外插入作用倾向于在错配序列中的正常双碱基对C3A4/G3T4(错配碱基对附近)中从小沟进行.与该配合物对含G:A错配的和正常的B-DNA序列的识别作用不同的是,对包含C:T错配碱基对的B-DNA序列的识别作用倾向于从小沟进行.这一点可能源于C:T碱基对结构的不同. 相似文献