Spin–orbit coupling in oxygen containing diradicals

Intermediate diradicals which occur in the Paterno–Büchi photocycloaddition and in the Norrish type I photoreactions have been calculated taking into account the spin–orbit coupling (SOC) between the singlet (S) and triplet (T) states. Reaction paths for the photocycloaddition of formaldehyde to ethene and the diradical products of the α-cleavage of cyclohexanone have been optimized by the MNDO CI method for a number of different singlet and triplet states. SOC integrals are calculated by an effective one-electron approximation. Intermediate diradicals in the Paterno–Büchi reaction and the SOC effects are also studied ab initio with CAS SCF geometry optimization in a TZV basis set. Both methods predict a large SOC matrix element between the S and T states in the course of the C–C attack, while the SOC integral is two orders of magnitude smaller for the diradical produced in the C–O attack. In the Norrish type I photoreaction the oxygen atom also produces some nonzero contribution to the SOC integral which governs intersystem crossing in a ·C–C· diradical. For the diradicals produced by the α-cleavage of cyclohexanone a vibronic interaction is responsible for the SOC mixing between the lowest S and T states. The importance of one-center versus two-center SOC contributions in diradicals is briefly discussed.     

木卫停泊轨道间低耗能小推力转移轨道设计方法研究

对木卫停泊轨道间的低耗能小推力转移轨道设计方法进行了研究,提出基于“类halo轨道截面”法的低耗能转移轨道参数化方法和基于配点法的多体Lambert问题求解算法,并利用全局优化算法得出了燃耗最少的初步优化结果;利用多体同伦法和固定近心点高度的多圈转移控制律得到了各段小推力转移轨道的有效设计结果.所提方法同样适用于其他天体间的转移轨道设计,为多体环境下低耗能小推力转移轨道提出了新的设计思路和方法.     

基于光学数据的地球同步轨道目标定初轨方法

初轨确定的目的主要有两个,一是为空间目标精密轨道计算提供初值,二是为空间目标轨道测量数据相互关联提供初值,其重要性不言而喻。根据地球同步轨道目标的轨道运行特征,在观测弧段内相对测站几乎保持相对静止。由于光学测角数据中缺乏测距的约束,在基于短弧段的光学测角数据采用传统的Laplace方法计算其初始轨道时,由于观测条件的病态性,迭代过程大多发散,难以得到收敛的初轨结果。鉴于上述原因,本文采用遍历搜索轨道半长轴的方法,提出了基于给定半长轴引入伪测距的初轨确定方法,经过仿真数据检验,该方法初轨确定成功率优于95%,有效地解决了地球同步轨道带近圆轨道目标初轨确定过程中迭代难以收敛的问题。

     

Full four‐component relativistic calculations of the one‐bond 77Se–13C spin‐spin coupling constants in the series of selenium heterocycles and their parent open‐chain selenides

Four‐component relativistic calculations of ⁷⁷Se–¹³C spin–spin coupling constants have been performed in the series of selenium heterocycles and their parent open‐chain selenides. It has been found that relativistic effects play an essential role in the selenium–carbon coupling mechanism and could result in a contribution of as much as 15–25% of the total values of the one‐bond selenium–carbon spin‐spin coupling constants. In the overall contribution of the relativistic effects to the total values of ¹J(Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin‐orbit ones (positive in sign), the latter being of less than 5%, as compared to the former (ca 20%). A combination of nonrelativistic second‐order polarization propagator approach (CC2) with the four‐component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of ¹J(Se,C). Solvent effects in the values of ¹J(Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants (ε 2.2–78.4) are next to negligible decreasing negative ¹J(Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of ⁷⁷Se–¹³C spin‐spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1–0.2‐Hz loss of accuracy. Copyright © 2014 John Wiley & Sons, Ltd.     

True spin and pseudo spin entanglement around Dirac Points in graphene with Rashba spin–orbit interaction

We analytically obtained the Schmidt decomposition of the entangled state between the pseudo spin and the true spin in graphene with Rashba spin–orbit coupling. The entangled state has the standard form of the Bell state, where the SU(2) spin symmetry is broken. These states can be explicitly expressed as the superposition of two nonorthogonal, but mirror symmetrical spin states entangled with the pseudo spin states. Because of the closely locking between the pseudo spin and the true spin, it is found that the orbit curve in the spin-polarization parameter space for the fixed equi-energy contour around Dirac points has the same shape as the $\delta \overrightarrow{k}$-contour. Due to the spin–orbit coupling that cause the topological transition in the local geometry of the dispersion relation, the new equi-energy contours around the new emergent Dirac Points can be obtained by squeezing the one around the original Dirac point. The spin texture in the momentum space around the Dirac points is analyzed under the Rashba spin–orbit interaction and it is found that the orientation of the spin polarization at each crystal momentum $\overrightarrow{k}$ is independent of the Rashba coupling strength.     

Existence of heteroclinic orbits in a novel three-order dynamical system

In this paper,we design a novel three-order autonomous system.Numerical simulations reveal the complex chaotic behaviors of the system.By applying the undetermined coefficient method,we find a heteroclinic orbit in the system.As a result,the Si’lnikov criterion along with some other given conditions guarantees that the system has both Smale horseshoes and chaos of horseshoe type.     

Spin polarization induced by an electric field in the presence of weak localization effects

We evaluate the spin polarization (Edelstein or inverse spin galvanic effect) and the spin Hall current induced by an applied electric field by including the weak localization corrections for a two-dimensional electron gas. We show that the weak localization effects yield logarithmic corrections to both the spin polarization conductivity relating the spin polarization and the electric field and to the spin Hall angle relating the spin and charge currents. The renormalization of both the spin polarization conductivity and the spin Hall angle combine to produce a zero correction to the total spin Hall conductivity as required by an exact identity. Suggestions for the experimental observation of the effect are given.     

Carlsson's rank conjecture and a conjecture on square-zero upper triangular matrices

Let k be an algebraically closed field and A the polynomial algebra in r variables with coefficients in k. In case the characteristic of k is 2, Carlsson [9] conjectured that for any DG-A-module M of dimension N as a free A-module, if the homology of M is nontrivial and finite dimensional as a k-vector space, then $2^r\le N$. Here we state a stronger conjecture about varieties of square-zero upper triangular $N\times N$ matrices with entries in A. Using stratifications of these varieties via Borel orbits, we show that the stronger conjecture holds when $N<8$ or $r<3$ without any restriction on the characteristic of k. As a consequence, we obtain a new proof for many of the known cases of Carlsson's conjecture and give new results when $N>4$ and $r=2$.     

Multifold factorizations of cyclic groups into subsets

Let $(G,+)$ be an abelian group. A finite multiset A over G is said to give a λ-fold factorization of G if there exists a multiset B over G such that each element of G occurs λ times in the multiset $A+B:=\{a+b:a\in A,b\in B\}$. In this article, restricting G to a cyclic group, we will provide sufficient conditions on a given multiset A under which the exact value or an upper bound of the minimum multiplicity λ of a factorization of G can be given by introducing a concept of ‘lcm-closure’. Furthermore, a couple of properties on a given factor A will be shown when A has a prime or prime power order (cardinality). A relation to multifold factorizations of the set of integers will be also glanced at a general perspective.