Nuclear spin species,spin statistical weights and rovibronic tunnelling splittings of non-rigid water hexamer

Powerful multinomial generating functions together with the character table of the six-dimensional hyperoctahedral wreath product group S₆[S₂] of the non-rigid water hexamer are employed to obtain the nuclear spin species, nuclear spin multiplets and the total nuclear spin statistical weights of the rovibronic-tunnelling levels for both deuterated and regular forms. The methods are composed of algebraic generating functions involving 531,441 nuclear spin functions for (D₂O)₆ in a group of 46,080 operations and 65 irreducible representations of the S₆[S₂] group. Although the deuterated form of the non-rigid water hexamer possesses nuclear spin populations in 58 of the 65 possible symmetries of tunnelling levels, for the regular water hexamer only 23 of the 65 symmetries are populated with nuclear spin functions. The tunnelling splitting correlations of rovibronic levels of the water hexamer have been obtained from the Saykally's semi-rigid (G₄) model to the fully non-rigid limit (G₄₆₀₈₀). The computed nuclear spin statistical weights for protonated form of (H₂O)₆ call for a reinterpretation of the previous assignment of the observed spectra. The results can also be applied to enumerate the hyperfine patterns using the nuclear spin multiplets and intensities in semi-rigid to fully non-rigid limits.     

一个改进的奇异摄动边值问题解的六次样条方法(英文)

基于六次样条插值,文章针对奇异摄动边值问题给出一个改进的六次样条方法.该方法的精度在所有内部结点达到八阶,在边界点达到五阶,通过一致收敛性分析和数值试验表明所给方法是有效的.     

Sextic spline method for the solution of a system of obstacle problems

We use sextic spline function to develop numerical method for the solution of system of second-order boundary-value problems associated with obstacle, unilateral, and contact problems. We show that the approximate solutions obtained by the present method are better than those produced by other collocation, finite difference and spline methods. A numerical example is given to illustrate practical usefulness of our method.     

Unrestricted Hartree-Fock spin density calculations with orthogonalized atomic orbitals on aza and nitroaromatic radical anions

The spin density distributions in some aza and nitroaromatic radical anions have been calculated using Löwdin's orthogonalized basis set of atomic orbitals in the Unrestricted Hartree-Fock method of Amos and Snyder. The present calculations lead to a satisfactory account of proton splittings in these radicals. Least squares analyses correlating the observed ¹⁴N splittings and the spin density results over completely localized nonorthogonal basis have been separately carried out for aza and nitroaromatic radical anions and the sigma-pi parameters thus obtained are discussed and compared with earlier estimates for these quantities. Unlike the earlier results, the present estimate of Q _NN ^N for aza and nitroaromatic radicals are not very much different from each other.     

The forbidden rotational Q branch of CH3SiF3: A study in internal rotation

The pure rotational spectrum driven by the small dipole moment produced perpendicular to the symmetry axis by centrifugal distortion has been investigated for CH₃SiF₃ in the ground vibrational state using a Fourier transform waveguide spectrometer. Between 10.9 and 17.0 GHz, four (k + 3 ← k) series in the Q branch have been measured in the lowest torsional state v₆ = 0 for k = 4, 5, 6, and 7 with 54 ? J ? 65. In each transition, the quantum number σ = 0, +1, −1 labelling the different torsional sub-levels is conserved. For given (J,k), splittings from ∼10 to ∼45 MHz have been observed between lines with different values of σ. The global data set includes the anticrossing molecular beam energy differences of [W.L. Meerts, I. Ozier, Chem. Phys. 71 (1982) 401-415] as well as the mm-wave R branch frequencies and (A₁ − A₂) splittings of [P. Dréan, J.-M. Colmont, J. Demaison, L. Dore, C. Degli Esposti, J. Mol. Spectrosc. 176 (1996) 23-27]). A good fit was obtained by varying 15 molecular parameters characterizing the torsion-rotation Hamiltonian H_TR for the vibrational ground state. Because of the strong correlation between two of the quartic torsion-distortion parameters (F_0,3K and D_0,Km) and a redundancy connecting the centrifugal distortion constants, four models were obtained yielding comparable fits. In each case, effective values were determined for the A-rotational constant and the height of the potential hindering the internal rotation. A high precision determination of the structural parameter ρ was made that is the same in all four models. For the off-diagonal quartic centrifugal distortion constant ε₀ and the sextic constants H_0,J, H_0,JK, H_0,KJ, and h_0,3, the differences in the values obtained in the two different reductions used have been explained in terms of the redundancy connecting these parameters. For σ = 0, +1, −1, the energy level pattern for (|k| = 3) is discussed for the case where the pure torsional energy splitting and the matrix elements off-diagonal in k are of comparable magnitude. A method is described of using an R branch study of the resulting σ-splittings for (|k| = 3) to probe the zeroth-order torsional Hamiltonian.     

Finite Nuclei in a Relativistic mean—Field Theory with quadratic Couplings

A quadratic scalar and vector coupling model proposed recently has been applied to finite nuclei.The calculated results are compared with those of the derivative scalar couling(DSC) model and the nonlinear Walecka model,The results show that the spin-orbit splittings are improved considerably by quadratic ouplings in contrast to the DSC model,However,the binding energy per nucleon,rms charge radius,as well as the spin-orbit splittings in the quadratic model are still small compared with those given by the nonlinear Walecka model and the experimental data.     

类锂离子体系高角动量态1s2ng(n=5～9)的精细结构的理论计算

利用全实加关联方法,以类锂等电子序列为研究对象,通过自旋－轨道相互作用和自旋－其它轨道相互作用算符的期待值计算了类锂离子等电子序列（Z=9～20）的高角动量1s2ng(n=5～9)激发态的精细结构劈裂.为了获得更精确的理论结果,在类氢近似下估算了高阶相对论修正和量子电动力学（QED）效应对精细结构的贡献,得到的结果与等电子序列规律符合的很好。     

On compact symplectic manifolds with Lie group symmetries

In this note we give a structure theorem for a finite-dimensional subgroup of the automorphism group of a compact symplectic manifold. An application of this result is a simpler and more transparent proof of the classification of compact homogeneous spaces with invariant symplectic structures. We also give another proof of the classification from the general theory of compact homogeneous spaces which leads us to a splitting conjecture on compact homogeneous spaces with symplectic structures (which are not necessary invariant under the group action) that makes the classification of this kind of manifold possible.

     

Theoretical and experimental investigation of (13)C relayed (2)H-(2)H-COSY 2D experiments: application to the analysis of weakly aligned solutes

We describe new NMR 2D experiments denoted DECADENCY for DEuterium CArbon DEuterium Nuclear Correlation spectroscopY dedicated to the analysis of anisotropic deuterium spectra. They belong to the class of X-relayed Y,Y-COSY 2D experiments that was initially explored in the case of a (1)H-X-(1)H fragment (I(X)=1/2) in isotropic medium. DECADENCY 2D experiments permit to correlate the quadrupolar doublets associated with two inequivalent deuterium nuclei in an oriented CD(2) fragment through heteronuclear polarization transfers. Two kinds of pulse sequences are described here using either a double INEPT-type or DEPT-type process. DECADENCY 2D experiments provide an interesting alternative to (2)H-(2)H COSY experiments when the geminal (2)H-(2)H total coupling (scalar and dipolar) is null or too small to provide visible cross-correlation peaks. Such a situation is typically observed for geminal deuteriums in prochiral or chiral molecules dissolved in chiral liquid crystals. The efficiency of these techniques is illustrated using dideuterated prochiral molecules, the phenyl[(2)H(2)]methanol and the 1-chloro[1-(2)H(2)]nonane, both dissolved in organic solutions of poly-gamma-benzyl-l-glutamate. The advantages of each sequence are presented and discussed. It is shown that the relative sign of the quadrupolar doublets can be determined.