Shift of proton magnetic shielding in ClH ··· Y dimers (Y = N2, CO,BF)

The change in the proton magnetic shielding constant of ClH on the formation of the linear hydrogen-bonded ClH?·?·?·?Y (Y?=?N₂,?CO,?BF) complexes was determined by GIAO ab initio computations at the B3LYP/aug-cc-pVQZ level of theory. The characteristic downfield shift of the isotropic proton magnetic resonance in the vibrationally red-shifted complexes (ClH?·?·?·?N₂, ClH?·?·?·?CO and ClH?·?·?·?BF) is significantly larger than in the blue-shifted complexes (ClH?·?·?·?OC and ClH?·?·?·?FB). These results are rationalized by considering the changes in the magnetic and electric contributions to the proton shielding in ClH.     

Spectroscopy and lasing of cryogenically cooled Yb, Na:CaF2

Absorption, photoluminescence and cw-lasing properties of a novel Na⁺-codoped Yb³⁺:CaF₂ laser crystal are investigated in the temperature range from 10 K to 290 K. Cryogenic cooling leads to the disappearance of the ground-state absorption in the spectral region above 1000 nm and a substantial increase of emission and absorption cross-sections. A particular advantage of the Yb³⁺, Na⁺-codoped CaF₂ crystal lies in the possibility of a direct pumping in the vicinity of the zero phonon line while nearly perfectly avoiding an overlap with the stimulated emission. Further advantages of the low-temperature operation are demonstrated by achieving a close to the theoretical limit slope efficiency of 92% in a cw-laser operation with an output coupler of 28%. By seeding stretched pulses from a femtosecond Yb fiber oscillator into a cryogenically cooled DPSS Yb³⁺,?Na⁺:CaF₂ regenerative amplifier, we obtain >3-mJ pulses at a 1-kHz repetition rate with a spectral bandwidth exceeding 12 nm. The pulses are compressed with a single grating compressor to 173 fs as verified by SHG FROG. Shaping of the spectral amplitude of the seed and active control of the higher-order phase is shown to be crucial for obtaining sub-200-fs pulses at multi-mJ energies.     

Blue and red shifts in Rg···HCN and Rg···HNC complexes (Rg=He,Ne, Ar,Kr)

The shift in the harmonic vibrational frequency of the H–C stretch of HCN on formation of the linear Rg···HCN complexes, and of the H–N stretch of HNC on the formation of Rg···HNC complexes (Rg?=?He, Ne, Ar, Kr), has been determined by ab initio computations. These shifts are in agreement with predictions from a model based on perturbation theory and involving the first and second derivatives of the interaction energy with respect to displacement of the H–C (H–N) bond length from its equilibrium value in the monomer. Small blue shifts were obtained for He···HCN, Ne···HCN and He···HNC, while red shifts were obtained for the other weakly bound complexes. These vibrational characteristics are rationalized by considering the balance between the interaction energy derivatives obtained from the perturbative model. For all complexes, the IR intensity of the H–C or H–N stretch was increased from the isolated monomer values on complexation.     

Structural and electronic properties of silver-doped gold clusters Au n Ag v (2 ≤ n ≤ 10; v = 0, ±1): comparison with pure gold clusters

The structural and electronic properties of silver-doped gold clusters Au _n Ag ^v (2?≤?n?≤?10; v?=?0,?±1) have been systematically investigated using density functional theory. The results show that the ground state optimal structures of the cationic and neutral clusters are found to be planar up to n?=?3 and 9, respectively. However, for the anionic clusters, no three-dimensional lowest-energy structures are obtained according to DFT calculations. The calculated binding energy and dissociation energy as a function of cluster size exhibit odd–even alternations. The natural population analysis indicates that in Au _n Ag ^v clusters charges transfer from the Ag atom to the Au frames. The trends for the vertical detachment energies, adiabatic electron affinities, adiabatic ionization potentials, and chemical hardness of Au _n Ag ^v clusters, as the cluster size increases, are studied in detail and compared with the available experimental data.     

In-plane London penetration depths near the critical temperature of Tl2Ba2Ca n−1Cu n O2n+4 and (Bi,Pb)2Sr2Ca n−1 Cu n O2n+4 (n=2,3)

From isothermalM(H) curves nearT _c , measured on polycrystalline Tl₂Ba₂Ca _n–1Cu _n O_2n +4 and (Bi, Pb)₂Sr₂Ca _n–1Cu _n O_2n+4 (n=2,3) samples, we deduce the in-plane penetration depths _ab as functions of temperature. An estimate according to the BCS weak-coupling clean-limit fit, which produces the data nearT _c very well, yields _ab(0)=3100 Å, 2320 Å 2210 Å, and 1960 Å for Bi₂Sr₂CaCu₂O₈, Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O₁₀, Tl₂Ba₂CaCu₂O₈, and Tl₂Ba₂Ca₂Cu₃O₁₀, respectively. A comparison between strong-coupling and weak coupling fitting curves clearly favours the weak-coupling temperature dependence of _ab nearT _c .     

(n,2n),(n,3n)反应激发函数的系统学研究

本文用包括平衡前发射在内的蒸发模型理论研究了(n,2n),(n,3n)反应的激发函数系统学.在对实验数据分析、拟合的基础上,得到一组较好的经验参数.利用这组参数计算得到的截面和实验结果符合较好.     

Entanglement Conditions for Mixed SU(2) and SU(1, 1) Systems

We derive a class of inequalities for detecting entanglement in the mixed SU(2) and SU(1,?1) systems based on the Schrödinger-Robertson indeterminacy relations in conjugation with the partial transposition. These inequalities are in general stronger than those based on the usual Heisenberg uncertainty relations for detecting entanglement. Furthermore, based on the complete reduction from SU(2) and SU(1,?1) systems to bosonic systems, we derive some entanglement conditions for two-mode systems. We also use the partial reduction to obtain some inequalities in the mixed SU(2) (or SU(1,?1)) and bosonic systems.     

A computational study of N2···HHeF: comparison with N2···HArF and N2···HKrF

A weakly bound linear complex of N₂ and HHeF was found to be stable with respect to the constituent monomers by ab initio calculations at various levels of theory (MP2, MP3, MP4(SDQ) and QCISD) using a 6-311++G(2d,2p) basis set. The complex N₂···HHeF was found to have a zero-point vibrational energy corrected binding energy of 14.5?kJ mol^?1 (QCISD) and exhibits a large harmonic vibrational frequency blue shift of 375?cm^?1 for the He–H stretching vibration mode, with a diminished infrared intensity for this mode on formation of the complex. The frequency shift for this mode was also found to be very sensitive to the level of theory employed for the calculation, and is rationalized by considering intermolecular electrostatic and charge-transfer effects. The results for N₂···HHeF are compared with corresponding results for the related complexes N₂···HArF and N₂···HKrF, both of which contain the same proton acceptor molecule.     

Mössbauer study of the HgBa2Ca n−1CunO2n+2 ceramics

The parameters of the electric-field gradient tensor at the copper, barium, and mercury sites in the HgBa₂Ca _n?1Cu_nO_2n+2 lattices (n=1,2,3) have been determined by Mössbauer emission spectroscopy on the ⁶⁷Cu(⁶⁷Zn), ¹³³Ba(¹³³Cs), and ¹⁹⁷Hg(¹⁹⁷Au) isotopes, and calculated in the point-charge approximation. An analysis of these results combined with available ⁶³Cu NMR data showed that the experimental and theoretical data can be reconciled by assuming that the holes originating from defects in the material are localized primarily on the sublattice of the oxygen lying in the copper plane [for HgBa₂Ca₂Cu₃O₈, in the plane of the Cu(2) atoms].     

A Mössbauer study of FeC2O4·2D2O below the néel temperature

From low-temperature Mössbauer measurement on FeC₂O₄·2D₂O the reported difference in quadrupole splitting from the simple dihydrate is inferred to be due to lattice effects. The Zeeman split spectrum has been analyzed taking into account the ambiguity problem and the hyperfine parameters were determined to be I.S.=1.22 mm/sec; Q.S.=1.93 mm/sec; =0.65 to 0.72; =90 to 83.1^o and =0 to 11.8^o. The principal electric field gradient axis lies along the crystal a-axis with V_YY and lying along the crystal b-axis. The crystal field parameters 10Dq, Ds and Dt have been determined to be 10500, 185 and 211 cm^–1, respectively.     

中重核14.5MeV (n,2n),(n,3n)反应截面的系统学计算

本文从中子核反应机制出发,讨论(n,2n),(n,3n)反应过程,给出约化截面的计算公式.按照系统学方法计算z=58—83的53个中重核的14.5MeV (n,2n),(n,3n)反应截面,计算结果与实验值符合较好.     

(n,2n)反应同质异能态截面比

在统计理论及考虑角动量守恒的激子模型的基础上,运用Monte Carlo方法计算(n,20)反应同质异能态截面比. 以⁵⁹Co(n,2n)⁵⁸Co、⁹³Nb(n,2n)⁹²Nb和¹⁸¹Ta(n,2n)¹⁸⁰Ta的3个反应道为例,计算从其阈能到20MeV能区的同质异能态截面比,并和已有实验数据做了比较,结果符合较好. 这表明本文提供的方法是计算(n,2n)反应同质异能态截面比的一种有效方法.     

Geometries and electronic properties of NbnV(0, ±1) (n = 1−6) clusters studied by density-functional theory

Using density functional theory (DFT) with valence basis set LANL2TZ to study the relative stabilities and electronic properties of the most stable structures of Nb _n V^(0,?±1) (n = 1?6) clusters. The ground state structures of Nb _n V ^(0,?±1) keep the similar geometric structure as the host Nb _n clusters. The doping of vanadium atom enhances the chemical activities of Nb _n clusters. The Nb₃V and Nb₆V are more stable than other clusters. The average binding energy of charged systems (Nb _n V⁺ and Nb _n V^? clusters) are generally larger than neutral Nb _n V clusters natural population analysis shows that there are charge transfers from niobium to vanadium atoms in the small Nb_1?4V, however, for larger clusters (Nb₅V and Nb₆V), the charge transfers are from vanadium to niobium atoms. The vertical and adiabatic ionization potentials (VIP and AIP) are estimated and the vertical one is more close to experimental results.     

93Nb(n,2n)92mNb反应截面测量

用活化法以^27Al(n,α)^24Na反应截面为中子注量标准，对14MeV能区中子引起的^93Nb(n,2n)^92mNb反应截面进行了测量。中子能量由硅探测器法测定。     

Tin-mZrmO2n(n=2-7，0≤m≤n)团簇结构和稳定性研究

应用密度泛函理论中的B3LYP方法对Tin-mZrmO2n (n = 2-7,0≤m≤n) 团簇的基态几何结构、相对稳定性和电子结构进行了理论研究.结果表明,与桥氧链接的Ti原子被Zr原子取代后形成的混合团簇较为稳定;在团簇尺寸一定的条件下（即n相同）,随着Zr原子数m的增加,团簇的结合能基本呈线性增大,团簇的稳定性增强;Ti、Zr、O原子之间发生了电荷转移现象,形成了稳定的Ti-O-Zr键.     

High-resolution electron microscopy and electron diffraction on Bi2Sr2-x La x Ca n Cu1+n O6+2n+δ

Solid solutions, Bi₂Sr_2-x La _x CuO₆₊ withx< 1.3 and Bi₂Sr_2-x La _x CaCu₂O₈₊ with probablyx<1.3 are reported. Both solid solutions show considerable nonlinear changes in the unit cell dimensions and a change in the modulation vector from 4.7b to 3.5b forx=0 andx=1.2, respectively. It is shown that Bi₂Sr_2-x La _x CaCu₂O₈₊ shows sometimes the absence of the 0.54 nm period alonga, whereas the modulation remains, suggesting both features not to be correlated. The investigation of the solid solution Bi₂Sr_2-x La _x CaCu₂O₈₊ with probablyx<1.3 are reported. Both solid solutions show considerable nonlinear changes in the unit cell dimensions and a change in the modulation vector from 4.7b to 3.5b forx=0 andx=1.2, respectively. It is shown that Bi₂Sr_2-x La _x CaCu₂O₈₊ is severly hampered by the presence of the n=0 structure in the reaction product when one starts with stoichiometric mixture. This can be overcome by adding extra Ca and heating directly just below the melting point. However addition of Ca to the mixture leads to changes in the solid solution range, because Ca can replace Sr.     

Structure of iron to 1 Gbar and 40, 000 K

First-principles calculations show that compression-induced electronic transitions produce a rich phase diagram featuring reentrant stability of the fcc phase with an extremum on the fcc to hcp boundary at 23?Mbar and 19?000?K, conditions similar to those expected at the center of super-Earth exoplanets. Transformations of hcp to fcc at 57?Mbar due to 4s to 3d electron transfer and from fcc to a body-centered structure at 320?Mbar due to hybridization of the 3d with the core 3p band are experimentally observable along a quasi-isentrope generated by laser-induced ramp compression.     

88Y(n,2n)反应截面研究

本工作用相同复合系统的核反应替代法获得了入射中子能量在10.3MeV到17.4MeV区间不稳定靶核⁸⁸Y(n,2n)核反应截面,并把该结果同我们的理论计算结果及Prestwood等人的实验和理论计算结果进行了比较,比较结果表明这种替代测量法值得研究.     

Dielectric relaxation of α-cyclodextrin-polyiodide complexes (α-cyclodextrin)2 · BaI2 · I2 · 8H2O and (α-cyclodextrin)2 · KI3 · I2 · 8H2O

The frequency and temperature dependence of the real (ε′) and imaginary (ε″) parts of the dielectric constant of the polycrystalline complexes (α-CD)₂ · Bal₂ · I₂ · 8H₂O and (α-CD)₂ · KI₃ · I₂ · 8H₂O (α-CD = α-cyclodetrin) have been investigated over the frequency and temperature ranges 0–100 kHz and 120–300 K, respectively. The temperature dependences of ε′, ε″ and the phase shift φ show two steps, two peaks and two minima, respectively, revealing the existence of two kinds of water molecule, the tightly bound and the easily movable water molecules, in both complexes. The first peak of (T) or the first minimum of φ(T) presents the transformation of flip-flop hydrogen bonds to the normal state. The second ε″ (T) peak or φ(T) minimum corresponds to the easily movable water molecules or to a partial transformation of tightly bound to easily movable water molecules. For T > 270K both samples show semiconductive behaviour with energy gaps of 1.84eV for the (α-CD)₂ · BaI₂ · I₂ · 8H₂O complex and 1.36eV for the (α-CD)₂ · KI₃ · I₂ · 8H₂O complex. The conductivity at room temperature decreases in the order: (α-CD)₂ · BaI₂ · I₂ · 8H₂O > (α-CD)₂ · LiI₃ · I₂ · 8H₂O > (α-CD)₂ · KI₃ · I₂ · 8H₂O > (α-CD)₂ · Cd_0.5 · I₅ · 26H₂O. The relaxation time varies in a Λ-like curve (from 120 to 250 K) and rises rapidly for temperatures greater than 250 K, indicating the process of ionic movements. The activation energies around the transition temperature 0.98–1.09 k _B T _trans for (α-CD)₂ · BaI₂ · I₂ · 8H₂O and 1.06-1.55 k _B T _trans for (α-CD)₂ · KI₃ · I₂ · 8H₂O reveal the greater stability of the α-K complex against that of the α-Ba complex.