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11.
The rotational spectra of nine isotopomers of dimethyl diselenide, CH3SeSeCH3, have been measured with a molecular-beam Fourier transform microwave spectrometer. The spectra were complex due to the presence of many isotopomers in natural abundance and the splitting caused by the interactions with two methyl internal rotors. The spectra were assigned and fit to experimental precision to an effective rotational Hamiltonian for molecules with two periodic internal motions. The spectra of the symmetric isotopomers are consistent with a C2 equilibrium structure. The rotational constants were used to determine the rs structure of the C-Se-Se-C frame with the results r(SeSe)=2.306(3) Å, r(SeC)=1.954(6) Å, ?(CSeSe)=99.8(2)°, ?(CSeSeC)=85.2(1)°. A barrier to internal rotation of the methyl groups of 395 ± 2 cm−1 was derived from the internal rotation splittings. 相似文献
12.
Tjalling J. Ypma 《Numerical Linear Algebra with Applications》1995,2(6):533-541
An algorithm for pre- or post-multiplication of a matrix by a plane rotation, using only three vector saxpy operations instead of the four vector operations usually considered necessary, is described. No auxiliary storage for overwriting is required. The method is shown to be numerically stable. 相似文献
13.
S.F. Lienin R. Brüschweiler R.R. Ernst 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,131(2):184-190
The viscosity-dependent retarding effect of a polymeric solvent on the rotation of small solute molecules is investigated by13C NMR relaxation measurements. It is found that the relaxation data of 1,3-dibromoadamantane in highly viscous polymeric chlorotrifluoroethene can be explained neither by isotropic nor by realistic anisotropic tumbling in a single environment. The experimental data are rationalized in terms of fast exchange between at least two environments with correlation times differing by up to two orders of magnitude. The study shows that a uniform retardation of molecular tumbling by a polymeric solvent, desirable for shifting the NMR observation window in studies of intramolecular mobility, is not always feasible. 相似文献
14.
We show that the composition of not only two SO(3,1) boosts, but also that of two SO(n,1) boosts for anyn 2, is basically an SO(2,1) problem and hence can be analysed completely using SL(2,R) matrices. By computing the expression for the Thomas/Wigner angle directly using SL(2,R) matrices we show that this approach results in considerable economy of algebra. 相似文献
15.
磺酞豚分子是一类极其重要的低毒超高效除草剂,有着十分重要的用途.研究分子的空间结构对于了解分子的构效关系十分重要.最近,我们测定的一系列分子的晶体结构[‘-’1表明,分子1、2、3晶体结构的空间群分别为PZ;儿、Pz、Pz,说明晶体中分别有对称元素(对称面或者对称中心),分子以对映体的形式存在于晶体中.由于磺酸豚分子本身不存在手性原子,由此推断磺酷服分子在晶体中存在的对映异构体是由内旋转阻碍产生的,因而应是构象异构体.本项研究工作的目的是应用分子力学方法,计算阻碍内旋转的能垒,从而找出分子内旋转时的最低… 相似文献
16.
近年来,分子内环加成反应已广泛用于甾体化合物全合成,其主要一步是由取代的苯并环丁烯热裂而成的5,6-二亚甲基-1,3-环己二烯发生区域专一和立体选择性的环加成反应,构成甾体骨架。现在用此法已合成了一系列消旋和光学活性的甾体化合物。 相似文献
17.
I. A. Ronova L. V. Dubrovina A. Yu. Kovalevskii C. Hamciuc M. Bruma 《Russian Chemical Bulletin》1998,47(7):1248-1256
Hindered rotation was considered in calculations of the conformational parameters of a series of polyheteroarylenes with bulky
side substituents by the Monte-Carlo method. Within the range of experimental errors, the results of calculations for several
polyarylates coincide with the values of conformational rigidity, determined from hydrodynamic experimental data. The proposed
procedure was used to estimate the rigidities of a number of polymers with bulky side substuents for which experimental determination
is difficult.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1287–1296, July, 1998. 相似文献
18.
研究了4-位苯基取代基旋转受阻和旋转自由的2,4,6-三苯基氧盐的光物理性质。实验结果表明,当4-位苯基取代基旋转受阻时,氧盐化合物在激发态时引起的分子内极化程度比4-位取代基旋转自由的氧盐化合物大,即在激发态时旋转受阻氧盐化合物发生的分子内电荷转移能力较强;4-位取代基旋转自由的化合物的荧光量子产率随溶剂粘度的增大而有所增大,但旋转受阻化合物在相同的条件下则出现相反的结果。实验结果还表明,4-位取代苯基旋转受阻对化合物的荧光发射不利。 相似文献
19.
从(-)-(1S,2R,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(I)和(-)-(1S,2S,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(Ⅱ)出发,合成了它们的醚类和取代苯甲酸酯类光学纯的衍生物。通过[α]D测定和构型分析,发现它们是含有3个手性碳(C1,C2和C4)的桥环化合物,其旋光性与构型的关系均符合可极化度多级圆球不对称性模型。 相似文献
20.
The molecular and electronic structure of the ground state of peroxyacetyl nitrate (PAN) was calculated by the unrestricted
Hartree-Fock-Roothaan method with the use of the standard 3–21G and 6–31G basis set. The potential curve of the internal rotation
about the peroxide bond of PAN was calculated with the 6–31G basis set. The curve contains two maxima. The ground state of
PAN is characterized by a structure in which groups of atoms adjacent to the peroxide bond lie in planes that are perpendicular
to each other (the dihedral angle ϱ(COON) is 89.9°). The calculated barriers to rotation are 19.6 and 66.8 kJ mol−1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 600–604, April, 1998. 相似文献