Applications of the Stochastic Adiabatic Approximation

In the previous paperi^[1], we have studied a class of nonlinear stochastic dynamical systems using the stochastic adiabatic approximation. A closed evolution equation for the slow variable u^t is obtained. In the present study, we use the methods proposed by the authors in Refs. [2] and [3] to treat the closed u^t equation which is derived by means of the new eliminating technique developed in Ref. [1] recently. Two important stochastic dynamical models, the simplified single-mode laser model and the stochastic Haken model, are treated concretely. The coupling effect of the additive and the multiplicative noise is found.     

Fluid simulations with localized boltzmann upscaling by direct simulation Monte-Carlo

In the present work, we present a novel numerical algorithm to couple the Direct Simulation Monte Carlo method (DSMC) for the solution of the Boltzmann equation with a finite volume like method for the solution of the Euler equations. Recently we presented in [14], [16], [17] different methodologies which permit to solve fluid dynamics problems with localized regions of departure from thermodynamical equilibrium. The methods rely on the introduction of buffer zones which realize a smooth transition between the kinetic and the fluid regions. In this paper we extend the idea of buffer zones and dynamic coupling to the case of the Monte Carlo methods. To facilitate the coupling and avoid the onset of spurious oscillations in the fluid regions which are consequences of the coupling with a stochastic numerical scheme, we use a new technique which permits to reduce the variance of the particle methods [11]. In addition, the use of this method permits to obtain estimations of the breakdowns of the fluid models less affected by fluctuations and consequently to reduce the kinetic regions and optimize the coupling. In the last part of the paper several numerical examples are presented to validate the method and measure its computational performances.     

Structure and polarization in the high Tc ferroelectric Bi(Zn,Ti)O3-PbTiO3 solid solutions

Theoretical ab initio and experimental methods are used to investigate the [Bi(Zn1/2Ti1/2)O3]x[PbTiO3]1-x solid solution. We find that hybridization between Zn 4s and 4p and O 2p orbitals allows the formation of short, covalent Zn-O bonds, enabling favorable coupling between A-site and B-site displacements. This leads to unusually large polarization, strong tetragonality, and an elevated ferroelectric to paraelectric phase transition temperature.     

[Fe/Cr]多层膜及掺入Si中介层后的层间耦合和磁电阻效应

用真空蒸镀方法制备了［Ｆｅ／Ｃｒ］，［Ｆｅ／Ｃｒ／Ｓｉ］和［Ｆｅ／Ｓｉ］多层膜．研究了Ｃｒ层、Ｓｉ层和Ｃｒ＋Ｓｉ层厚度变化对层间耦合和磁电阻的影响．Ｆｅ层厚为２ｎｍ，Ｃｒ层厚度变化存在耦合振荡和巨磁电阻及其振荡．磁电阻值为１４.６％（４.２Ｋ）．在Ｃｒ层中加入一半Ｓｉ层或全部由Ｓｉ层替代，振荡消失，磁电阻减小到千分之几．根据掺Ｓｉ层后多层膜的电阻率变化，认为Ｓｉ加入使非磁层中自由电子数减少，随之极化效应也变弱，导致振荡消失，磁电阻大为降低 关键词：     

Synthesis of benzopyrano[4,3-b](N-arylsulfonyl)indoles and benzopyrano[3,4-b](N-arylsulfonyl)indoles via intramolecular palladium-catalyzed aryl–aryl coupling reaction

A series of benzopyrano[3,4-b](N-arylsulfonyl) indole derivatives and benzopyrano[4,3-b](N-arylsulfonyl) indole derivatives were synthesized from 2- or 3-methylindole via intermolecular S( N )2 reaction and subsequent intramolecular palladium-catalyzed aryl-aryl coupling reaction for the first time. It was suggested that, besides using the Fischer cyclization, benzopyrano[4,3-b]indoles and benzopyrano[3,4-b]indoles could also be prepared via intermolecular S( N )2 reaction and sequential intramolecular palladium-catalyzed coupling reaction.     

[OsⅣ（N）（NH3）4]（CF3SO3）3电化学还原过程的原位FTIR光 …

运用原位ＦＴＩＲＳ,ＵＶ／Ｖｉｓ和电化学方法研究了乙腈溶液中「ＯｓⅣ（Ｎ）（ＮＨ３）４」（ＣＦ３ＳＯ３）３在ＧＣ和Ｐｔ电极上的还原过程。结果首次在Ｐｔ电极上检测到桥氮物种υ（Ｎ≡Ｎ）的红外谱峰,位于２０１９和１９７０ｃｍ＾－１附近,分别指认为「Ⅲ,Ⅱ」和「Ⅱ,Ⅱ」混合价桥氮俄络合物。为进一步探讨桥氮偶联过程提供了新的谱学数据。     

On the cutoff parameter in the translation-invariant theory of the strong coupling polaron (response to comments [8] on the paper V.D. Lakhno,SSC 152 (2012) 621)

The paper is a reply to the arguments adduced by the authors of [8] against the results obtained by the author in [6], [7]. It is shown that these arguments are based on the erroneous approach made in [8] to the strong coupling limit when the cutoff parameter is introduced in the theory.     

Explorative computational study of the singlet fission process

Different ab initio methods, namely multi-reference and nonorthogonal configuration interaction techniques, are explored for their applicability in studying the singlet fission problem. It has been shown for 2-methyl-1,5-hexadiene that the ¹TT state can be identified using multi-reference techniques. The geometrical and vibrational properties of the ¹TT state are such that they can be approximated with those of the ⁵TT state. A proof of principle is given for the calculation of the singlet fission pathway driven by nuclear motion: efficient singlet fission can take place if the ¹TT and S₁ states are close in energy with a large non-adiabatic coupling matrix element at the S₁ geometry, and the energy of the S₀ state is well below that of the ¹TT state at the ¹TT geometry.

The nonorthogonal configuration interaction method was used to treat a tetracene trimer. It has been shown that the first excited states can be interpreted as delocalised states; interaction with charge-transfer base states plays an important role. The ¹TT states are localised on one pair of molecules. The electronic coupling between the diabatic S[n] and ¹TT[m] states is in the meV range, confirming previous estimates. The charge-transfer base states enhance the coupling between the S[1]/S[2] and ¹TT[2] excited states.     

Eight-quark interactions as a chiral thermometer

A NJL Lagrangian extended to six [1–3] and eight quark interactions [4] is applied to study temperature effects [5] (SU(3) flavor limit, massless case), and [6] (realistic massive case). The transition temperature can be considerably reduced as compared to the standard approach, in accordance with recent lattice calculations [7]. The mesonic spectra built on the spontaneously broken vacuum induced by the’ t Hooft interaction strength, as opposed to the commonly considered case driven by the four-quark coupling, undergoes a rapid crossover to the unbroken phase, with a slope and at a temperature which is regulated by the strength of the OZI violating eight-quark interactions. This strength can be adjusted in consonance with the four-quark coupling and leaves the spectra unchanged, except for the sigma meson mass, which decreases. A first order transition behavior is also a possible solution within the present approach.     

Generalized Projective Synchronization between Two Complex Networks with Time-Varying Coupling Delay

Generalized projective synchronization （GPS） between two complex networks with time-varying coupling delay is investigated. Based on the Lyapunov stability theory, a nonlinear controller and adaptive updated laws are designed. Feasibility of the proposed scheme is proven in theory. Moreover, two numerical examples are presented, using the energy resource system and Lü＇s system [Physica A 382 （2007） 672] as the nodes of the networks. GPS between two energy resource complex networks with time-varying coupling delay is achieved. This study can widen the application range of the generalized synchronization methods and will be instructive for the demand supply of energy resource in some regions of China.     

Ferromagnetism in Mn-doped GaN nanowires

Using density functional theory we show that the magnetic coupling of Mn atoms in the nanowires, unlike that in the thin film, is ferromagnetic. This ferromagnetic coupling, brought about due to the confinement of electrons in the radial direction and the curvature of the Mn-doped GaN nanowires' surface, is mediated by N as is evidenced from the overlap between Mn 3d and N 2p states. Calculations of the anisotropic energy further show that the magnetic moment orients preferably along the [1010] direction while the wire axis points along the [0001] direction.     

Multiple quantum spin counting techniques with quadrupolar nuclei

Phase incremented and continuous irradiation multiple spin correlation methods are applied to spin [Formula: see text] nuclei with small quadrupole couplings such as (7)Li in LiCl and are shown to successfully produce a coherently coupled dipolar spin network. Application to the analogous Na salt shows successful spin correlation evolving at a slower rate due to the weaker homonuclear dipolar coupling strength between Na nuclei. The results are analysed using a statistical approach. Spin counting is non-trivial as not only multiple quantum coherences between spins are generated but also within the quadrupolar spin levels. Na(2)C(2)O(4) is investigated as a material with non-negligible quadrupole coupling and it is in this limit that the spin correlation techniques are found to break down.     

Syntheses of novel diaryl[d,f ][1,3]diazepines via one-pot Suzuki coupling followed by direct ring closure with carboxylic acids

A series of novel and diverse diaryl[d,f][1,3]diazepines were designed and synthesized to expand the pharmaceutical utility of the [6,7]bicyclic molecular skeletons. The facile synthesis involved two key steps: a one-pot Suzuki coupling to construct the bi-aryl intermediates from corresponding halides, and a ring closure by direct condensation with carboxylic acids.     

The superconducting specific heat jump of UBe13 and a narrow peak in the electronic density-of-states

The superconducting specific heat jump for the s-f; hybridization model of UBe₁₃ of Overhauser and Appel [2] is calculated. The narrow peak in the density-of-states is found to enhance the size of the jump relative to the BCS value of 1.43, but in weak coupling the increase is insufficient to agree with the measured value for UBe₁₃. The Kondo lattice model of Razafimandimby, Fulde and Keller [9] is considered as a possible modification, but in weak coupling a simple estimate shows that this cannot increase the specific heat jump significantly. It is speculated, however, that a consistent picture may still be possible with conventional strong coupling corrections.     

Sensitivity-enhanced double-TROSY experiment for simultaneous measurement of one-bond 15N-1H, 15N-13C' and two-bond 1H-13C' couplings

A recently published experiment for the measurement of 1JHN, 1JNC', and 2JHC' coupling constants [J. Am. Chem. Soc. 125 (2003) 11504] was modified to yield a double-TROSY experiment which selects 1 of the 16 multiplet components from a 15N-HSQC spectrum recorded of a uniformly 15N/13C-labelled protein. Subspectra containing any 1 of the 16 multiplet components can be generated allowing accurate coupling constant measurements. The experiment is sensitivity enhanced, turning all magnetization components precessing during the evolution time into observable magnetization during the detection time. The experiment is discussed with regard to the previously published alpha/beta-filtered HN(alpha/beta-NC'-J) experiment [J. Magn. Reson. 140 (1999), 32] which measures the same coupling constants.     

Magnetic properties of charged spin-1 Bose gases with ferromagnetic coupling

The magnetic properties of a charged spin-1 Bose gas with ferromagnetic interactions are investigated within mean-field theory. It is shown that a competition between paramagnetism, diamagnetism and ferromagnetism exists in this system. It is shown that diamagnetism, being concerned with spontaneous magnetization, cannot exceed ferromagnetism in a very weak magnetic field. The critical value of reduced ferromagnetic coupling of the paramagnetic phase to ferromagnetic phase transition [Formula: see text] increases with increasing temperature. The Landé-factor g is introduced to describe the strength of the paramagnetic effect which comes from the spin degree of freedom. The magnetization density [Formula: see text] increases monotonically with g for fixed reduced ferromagnetic coupling [Formula: see text] as [Formula: see text]. In a weak magnetic field, ferromagnetism makes an immense contribution to the magnetization density. On the other hand, at a high magnetic field, the diamagnetism tends to saturate. Evidence for condensation can be seen in the magnetization density at a weak magnetic field.     

Sulfonium-aided coupling of aromatic rings via sigmatropic rearrangement

Biaryl synthesis continues to occupy a central role in chemical synthesis. From blockbuster drug molecules to organic electronics, biaryls present numerous possibilities and new applications continue to emerge. Transition-metal-catalyzed coupling reactions represent the gold standard for biaryl synthesis and the mechanistic steps, such as reductive elimination, are well established. Developing routes that exploit alternative mechanistic scenarios could give unprecedented biaryl structures and expand the portfolio of biaryl applications. We have developed metal-free C–H/C–H couplings of aryl sulfoxides with phenols to afford 2-hydroxy-2′-sulfanylbiaryls. This cascade strategy consists of an interrupted Pummerer reaction and [3,3] sigmatropic rearrangement. Our method enables the synthesis of intriguing aromatic molecules, including oligoarenes, enantioenriched dihetero[8]helicenes, and polyfluorobiaryls. From our successes in aryl sulfoxide/phenol couplings and a deeper understanding of sigmatropic rearrangements for biaryl synthesis, we have established related methods, such as aryl sulfoxide/aniline and aryl iodane/phenol couplings. Overall, our fundamental interests in underexplored reaction mechanisms have led to various methods for accessing important biaryl architectures.     

分子间相互作用对核酸碱基中17O屏蔽张量与四极耦合常数影响的理论计算研究

通过高精度量子化学理论计算的方法研究了分子间弱的非键相互作用对胸腺嘧啶、尿嘧啶、胞嘧啶和鸟嘌呤四种核酸碱基中~(17)O核的屏蔽张量(σO)和四极耦合常数(QCC)的影响.计算结果表明分子间强的氢键作用以及弱的范德华(vd W)相互作用都对~(17)O核的化学位移(δO)具有较大的影响.随着分子间氢键作用的逐渐增强,δO逐渐减小,当采用包含所有弱相互作用的周期性模型进行计算时,理论结果与实验值吻合.进一步的电荷分析显示,~(17)O核化学位移的减小主要是由于分子间氢键作用强度增加导致~(17)O原子的负电荷密度逐渐增加.此外,计算结果表明碱基中分子间氢键网络和弱的范德华作用对碱基~(17)O QCC也具有显著的影响.周期性模型下,碱基上氧原子的局域结构环境得到平衡,~(17)O QCC达到最小值,与实验结果最为接近.以核酸碱基为例,说明了分子间的氢键网络以及分子间弱的相互作用对于准确计算生物样品的核磁共振(NMR)参数非常重要,以小的团簇模型来计算生物体系的核磁参数将会产生较大的偏差.     

Thin film Co[TCNE]2 and VyCo1−y[TCNE]2 magnetic materials

A chemical vapor deposition method has been developed for the synthesis of both solvent-free Co[TCNE]₂ and V_yCo_1−y[TCNE]₂ thin films. Both materials have been previously synthesized by solution methods, but contain solvent. The Co[TCNE]₂ thin films were characterized by infrared spectroscopy and magnetic studies, and albeit solvent-free were determined to be similar to the analogous solution-prepared samples as they are paramagnetic with slight antiferromagnetic coupling. In contrast to the solution-based synthesis, V_yCo_1−y-[TCNE]₂ showed no dependence of coercive field based on the composition of the films, even though infrared spectroscopic data indicates formation of a solid-solution thin film, and not a physical mixture.     

An electron paramagnetic resonance study of the tetragonally distorted [Formula: see text] ion in [Formula: see text] and [Formula: see text

Chromium-doped [Formula: see text] and [Formula: see text] have been studied by both EPR and ENDOR spectroscopy. [Formula: see text] ions enter the fluorite structure in distorted substitution cation sites. In both matrices the distortion observed is tetragonal. X- and Q-band EPR measurements at temperatures between 4 and 300 K allowed us to determine the ion symmetry and the following spin-Hamiltonian parameters: [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text] for [Formula: see text]; and [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text] for [Formula: see text]. For [Formula: see text], the weak superhyperfine interaction of [Formula: see text] with the surrounding [Formula: see text] ions has been studied by both EPR and ENDOR techniques for [Formula: see text]. No ENDOR signals were detected for [Formula: see text]. The results are tentatively explained in terms of a Jahn - Teller effect corresponding to [Formula: see text] coupling strongly stabilized by lattice stresses, although other possible origins for the distortion cannot be completely ruled out.