CuH分子A1∑+态的寿命和预解离研究

A combined cavity ringdown (CRD) and laser induced fluorescence (LIF) spectroscopic study on the A¹∑⁺-X¹∑⁺ transition of CuH has been presented.The CuH molecule,as well as its deuterated isotopologue CuD,are produced in a supersonic jet expansion by discharging H₂(or D₂) and Ar gas mixtures using two copper needles.Different profiles of relative line intensities are observed between the measured LIF and CRD spectra,providing an experimental evidence for the predissociation behavior in the A¹∑⁺ state of CuH.The lifetimes of individual upper rotational levels are measured by LIF,in which the J''-dependent predissociation rates are obtained.Based on the previous theoretical calculations,a predissociation mechanism is concluded due to the strong spin-orbit coupling between the A¹∑⁺ state and the lowest-lying triplet ³∑⁺ state,and a tunneling effect may also be involved in the predissociation.Similar experiments are also performed for CuD,showing that the A¹∑⁺ state of CuD does not undergo a predissociation process.     

Determination of Astrophysical 13N(p,γ)14O S-factors from the Asymptotic Normalization Coefficient of )14C → 13C + n

The angular distribution of the ¹³C(d,p)¹⁴C reaction is reanalysed using the Johnson--Soper approach. The squared asymptotic normalization coefficient (ANC) of virtual decay ¹⁴C →¹³C + n is then derived to be 21.4 ± 5.0fm^-1. The squared ANC and spectroscopic factor (SF) of ¹⁴O → ¹³N + p are extracted to be 30.4 ± 7.1fm^-1 and 1.94 ± 0.45, respectively. The astrophysical S-factors and reaction rates of ¹³N(pγ)¹⁴O are determined from the ANC of ¹⁴O → ¹³N + p using the R-matrix approach.     

Influence of rotational excitation and collision energy on the stereo dynamics of the reaction： N（4S）＋H2 （v = 0, j = 0, 2, 5, 10） →NH（X3∑-）＋H

The N+H₂ reaction has attracted a great deal of attention from both the experimental and the theoretical community, and most of the attention has been paid to the first excited state N(²D) atoms in collisions with hydrogen molecules and the scalar properties of the reaction. In this paper, we study the stereo dynamical properties and calculate the reaction cross sections of the N(⁴S) + H₂ (v=0, j=0, 2, 5, 10) → NH(X³Σ^-) + H using the quasi-classical trajectory (QCT) method on an accurate NH₂ potential energy surface (PES) reported by Poveda and Varandas [Poveda L A and Varandas A J C 2005 Phys. Chem. Chem. Phys. 7 2867], in a collision energy range of 25 kcal·mol^-1-140 kcal·mol^-1. Results indicate that the reactant rotational excitation and initial collision energy both have a considerable influence on the distributions of the k-j′ correlation, the k-k′-j′ correlation and k-k′ correlation. The differential cross section is found to be sensitive to collision energy.     

Spectroscopic investigations on NO+(x1∑+,a3∑+,A1Ⅱ) ion using multi-reference configuration interaction method and correlation-consistent sextuple b

Three low-lying electronic states (x¹∑⁺,a³∑⁺,and A¹Ⅱ) of NO⁺ ion are studied using the complete active space self-consistent-field (CASSCF) method followed by highly accurate valence internally contracted multi-reference configuration interaction (MRCI) approach in combination of the correlation-consistent sextuple basis set augmented with diffuse functions, aug-cc-pV6Z. The potential energy curves (PECs) of the NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) are calculated. Based on the PECs, the spectroscopic parameters R_e, D_e, ω_e, ω_eχ_e, α _e, B_e, and D₀ are reproduced, which are in excellent agreement with the available measurements. By numerically solving the radial Schrödinger equation of nuclear motion using the Numerov method, the first 20 vibrational levels, inertial rotation and centrifugal distortion constants of NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) ion are derived when the rotational quantum number J is equal to zero (J = 0) for the first time, which accord well with the available measurements. Finally, the analytical potential energy functions of these states are fitted, which are used to accurately derive the first 20 classical turning points when J = 0. These results are compared in detail with those of previous investigations reported in the literature.     

1,3-二烷基咪唑离子液体-水二元混合物的溶致显色参数和优先溶剂化行为

Binary mixtures of 1,3-dialkylimidazolium based ionic liquids (ILs) and water were selected as solvent systems to investigate the solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators at 25℃. Empirical solvatochromic parameters, dipolarity/polarizability (π^*), hydrogen-bond donor acidity (α), hydrogen-bond acceptor basicity (β), and Reichardt''s polarity parameters (E_T^N) were measured from the ultraviolet-visible spectral shifts of 4-nitroaniline, 4-nitroanisole, and Reichardt''s dye. The solvent properties of the IL-water mixtures were found to be influenced by IL type and IL mole fraction (x_IL). All these studied systems showed the non-ideal behavior. The maximum deviation to ideality for the solvatochromic parameters can be obtained in the xIL range from 0.1 to 0.3. For most of the binary mixtures, the π^* values showed the synergistic effects instead of the E_T^N, α and β values. The observed synergy extent was dependent on the studied systems, such as the dye indicator and IL type. A preferential solvation model was utilized to gather information on the molecular interactions in the mixtures. The dye indicator was preferentially solvated on the following trend: IL >IL-water complex >water.     

窄带隙KNb1-xFexO3-δ的室温铁磁性

We have investigated the structure, optical and magnetic properties of ferroelectric KNb_1-xFexO_3-δ (X=0, 0.01, 0.03, 0.05, 0.10, 0.15, 0.20, 0.25) synthesized by a traditional solid-state reaction method. According to the X-ray diffraction and the results of Rietveld refinement, all the samples maintain orthorhombic distorted perovskite structures with Amm2 space group without any secondary phase, suggesting the well incorporation of Fe ions into the KNbO₃ matrix. With the increase of Fe concentration, the band gap of each sample is decreased gradually, which is much smaller than the 3.18 eV band gap of pure KNbO₃. Through X-ray photoelectron spectrum analysis, the increased density of oxygen vacancy and Fe ions may be responsible for the observed decrease in band gap. Compared with the pure KNbO₃, Fe doped samples exhibit room-temperature weak ferromagnetism. The ferromagnetism in KNb_1-xFexO_3-δ with low-concentration dopants (X=0.01-0.10) can be attributed to the bound magnetic polaron mediated exchange. The enhancement of magnetism for the high-concentration (X=0.10-0.20) doped samples may arise from the further increase of magnetic Fe ions.     

Intrinsic tunneling study of underdoped Bi2Sr2-xLaxCuO6+δ superconductors

We report on a tunneling study of underdoped submicron Bi₂Sr_2-xLa_xCuO_6+δ (La-Bi2201) intrinsic Josephson junctions (IJJs), whose self-heating is sufficiently suppressed. The tunneling spectra are measured from 4.2 K up to the pseudogap opening temperature of T^* = 260 K. The gap value found from the spectral peak position is about 35 meV and has a weak temperature dependence both below and above the superconducting transition temperature of T_c = 29 K. Since the superconducting gap should have a value of 10-15 meV, our results indicate that the pseudogap (～35 meV) plays an important role in the underdoped La-Bi2201 intrinsic tunneling spectroscopy down to the lowest temperature of 4.2 K. However, the contribution of the superconducting gap can be separated by normalizing the spectra to the one near and above T_c, which shows that the IJJs can be a useful tool for the study of the electronic properties of the La-Bi2201 cuprate superconductors.     

P-branch emission spectra of the A1Π-X1Σ+ system of IrN

The P-branch emission spectra of (4,1) and (3,1) bands of the A¹Π-X¹Σ⁺ system of IrN molecule are studied using an analytical formula which is derived from elementary expression of molecular total energy by taking multiple spectral differences. It not only reproduces the known experimental transition lines, but also predicts the unknown spectral lines up to J= 80 for each band by using a group of fifteen known experimental transition lines.     

THE TWO-BOSON SCATTERING PHASE SHIFTS IN THE GENERAL φ6 THEORY WITH THE GAUSSIAN WAVE-FUNCTIONAL APPROACH

The two-particle scattering phase shifts with a λφ⁴ +ξφ⁶ interaction are com-puted in (1 + 1) and (2 + 1) dimensions using the Gaussian wave-functional approach.Through numerical analysis, we give the phase-shift curves with respect to the scat-tering energy for most cases of this theory. In (1 + 1) and (2 + 1 ) dimensions, for the symmetry vacuum the phase shifts are positive or negative depending on the signs of the renormalized parameter, while for the asymmetric vacuum the phase shifts are negative.     

RAFT控制合成PCL/PVP共聚物及其胶束行为的亲水链依赖性

A range of poly(ε-caprolactone)/poly(N-vinyl-2-pyrrolidone) amphiphilic block copolymers with well-de ned hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chain transfer polymerization method. The composition and struc-ture of the targeted resultants were characterized with ¹H NMR, ¹³C NMR, FT-IR spec-troscopy and gel permeation chromatography. The various block copolymers were success-fully employed to fabricate the spherical micelle with core-shell morphological structure. The poly(N-vinyl-2-pyrrolidone) block-dependent characteristics of the copolymeric micelles were investigated by uorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The solubilization of the hydrophobic ibuprofen as a model drug in the micelle solution was also explored. It was found that the drug loading contents are related to the micellar morphology structure determined by hydrophilic chain length in the copolymer.     

天然丰度的N-磷酰化氨基酸的15N NMR 研究

采用¹⁵N-¹H的2D HSQC、HMBC实验方法,测定了天然丰度的N-磷酰化氨基酸样品在溶液中的¹⁵N化学位移δ_N及偶合常数J_N-P,J_N-H. 实验表明：对于¹⁵N天然丰度样品,这是一种快速有效的实验方法. 研究发现：N-酰化后的氨基酸,其δ_N以及与氮原子直接相连的质子¹H的化学位移均发生十分明显的高场位移,而偶合常数¹J_N-P,¹J_N-H的变化与化合物构型相关联 .     

Al and Cu NMR study in UCu5Al

We have studied the microscopic properties of the tetragonal UCu₅Al Kondo compound by ²⁷Al and ^63,65Cu NMR in the paramagnetic state. NMR and susceptibility measurements performed on the powdered sample, but oriented along the applied field, showed χ>χ. Plots of K(T) against χ(T) at temperatures T≥100 K yield the transferred hyperfine fields of +5.9 kOe/μ_B for ²⁷Al nuclei, and +5.3 and −7.0 kOe/μ_B for ⁶⁵Cu nuclei in crystallographically inequivalent Cu(2) and Cu(1) sites, respectively. The Knight shift vs. susceptibility plots for T<100 K exhibit a deviation from the linear behaviour (absolute values of shifts become smaller than expected). We attribute this finding to the crystalline electric field effect in similar way as it was reported for several Ce-based compounds. The random distribution of the Al and Cu(2) atoms in the crystal lattice we consider as a reason of an unusual broadening of the NMR spectra, particularly at low temperatures.     

Hydroxyl Substituent Effects on 13C NMR Spectra of 4a-Methyl Octahydrophenanthrenes

The ¹³C NMR spectra of nine 4a-Methyl Octahydrophenanthrols are reported, and their chemical shifts are compared with those of the parent hydrocarbon and correlated against structural parameters. Two new parameters for β interactions are proposed and a α benzylic parameter is analysed. An extension to unsaturated six-membered rings skeletons is also tempted. Predictions for 30 carbons were carried out with an average error of 0.34 ppm.     

13C NMR Chemical Shifts and CH Coupling Constants of Substituted 4-Ylidenebutenolides

The ¹³C chemical shifts and CH coupling constants for 6 substituted 4-ylidenebutenolides are reported. The CH coupling constants are useful in helping to determine the stereochemistry of the substituted exocyclic double bond.     

13C NMR Chemical Shifts of Heterocycles: Empirical Substituent Effects in 5-Halomethylisoxazoles

Evaluation by empirically derived equations for the Substituent effect (α, β, γ, δ) on the ¹³C NMR chemical shifts for C-3, C-4. C-5 and halomethyl-substituent carbon (C-6) in isoxazoles 1-5 [where C-3 substituent (R¹) = H, alkyl or phenyl, C-4 Substituent (R²) = H, alkyl, and C-5 substituent (R³) = di-or trihalomethyl, methyl and H], taking as reference the compound la, is reported. From the calculated values for the α, β, γ, δ effects for each substituent it was possible to estimate the chemical shift of each carbon of the compounds 1–5. The ¹³ C chemical shifts of the C-3, C-4, C-5, C-6 of these compounds, can be estimated with good precision: 94% of the calculated chemical shifts are found to be within ±1.0ppm, and 100% are found to be within ±1.5ppm.     

利用基于~1H NMR的代谢组学分析研究重离子辐射对大鼠额叶皮质区的影响

太空辐射尤其是重离子辐射可造成DNA的破坏、细胞死亡、以及一些癌症的发生,是人类深空探索进程中急需克服的难题. 本文通过重离子加速器产生¹²C⁶⁺重离子束对大鼠头部进行一定剂量的辐射,模拟空间重离子辐射对中枢神经系统(CNS)的生物学效应. 采用基于¹H NMR的代谢组学方法对辐射大鼠大脑额叶皮质区进行了测定分析,结合数据的统计分析和检验,发现了包括一些重要CNS神经递质在内的代谢物含量发生明显变化. 这些代谢物主要为：牛磺酸、乳酸、谷氨酸、4-氨基丁酸、以及磷酸胆碱等. 结合差异蛋白质组结果分析,包括4-氨基丁酸、谷氨酸、乳酸、牛磺酸等在内的代谢物参与的主要生物途径,如神经递质的合成途径,以及神经递质受体介导的信号途径可能受重离子辐射的负面影响. 这些发现将为进一步阐明重离子辐射效应的分子机制提供有利信息,从而为从生物学途径探寻有效重离子辐射防护措施提供依据.     

Solid-State Rb NMR Study in Powdered RbMnCl3

Structural phase transition at 290 K and the implication on the intermediate phase above 290 K in powdered RbMnCl₃ are observed by using a solid-state ⁸⁷Rb NMR spectroscopy. Quadrupole coupling constants (e²qQ/h), the asymmetry parameters (η), and the relative peak intensities for two physically nonequivalent Rb sites, Rb(I) and Rb(II), are determined from nonlinear least-squares fits to the ⁸⁷Rb NMR powder patterns in the temperature range from 260 to 330 K. Quadrupole coupling constants and the asymmetry parameters are examined for the detection of the phase transition resulting in a significant structural change in the Rb(II) site. In addition, changes in the relative peak intensity between the Rb(I) and Rb(II) sites seem to suggest the existence of an anomalous intermediate phase, which is complemented by the differential scanning calorimetry and X-ray diffraction studies.     

A C solid-state NMR analysis of vitamin D compounds

¹³C cross-polarization/magic-angle spinning (CP/MAS) solid-state NMR spectroscopy has been employed to analyze four vitamin D compounds, namely vitamin D3 (D3), vitamin D2 (D2), and the precursors ergosterol (Erg) and 7-dehydrocholesterol (7DHC). The ¹³C NMR spectrum of D3 displays a doublet pattern for each of the carbon atoms, while that of Erg contains both singlet and doublet patterns. In the cases of 7DHC and D2, the ¹³C spectra display various multiplet patterns, viz. singlets, doublets, triplets, and quartets. To overcome the signal overlap between the ¹³C resonances of protonated and unprotonated carbons, we have subjected these vitamin D compounds to 1D ¹H-filtered ¹³C CP/MAS and {¹H}/¹³C heteronuclear correlation (Hetcor) NMR experiments. As a result, assisted by solution NMR data, all of the ¹³C resonances have been successfully assigned to the respective carbon atoms of these vitamin D compounds. The ¹³C multiplets are interpreted due to the presence of s-cis and s-trans configurations in the α- and β-molecular conformers, consistent with computer molecular modeling determined by molecular dynamics and energy minimization calculations. To further characterize the ring conformations in D3, we have successfully extracted chemical shift tensor elements for the ¹³C doublets. It is demonstrated that ¹³C solid-state NMR spectroscopy provides a robust and high sensitive means of characterizing molecular conformations in vitamin D compounds.     

K+-Na+二次离子交换制作玻璃波导

通过数值计算模拟了K⁺Na⁺二次扩散玻璃波导的折射率轮廓,阐述了利用K⁺Na⁺二次离子交换的方法,在BK7玻璃上制作波导的过程,分析了极化率不同的扩散离子对的选择对波导有效折射率变化的影响,以及扩散平衡时体积变化对表面折射率的影响,描述了扩散引起的波导内部诱导应力变化设计了测试波导损耗以及波导表面折射率改变的实验装置,对尺寸10mm×10mm×1.5mm和10mm×5mm×1.5mm两组BK7玻璃基片上的玻璃波导进行了测试,测试结果与理论吻合较好.     

Vibrational and Rotational Spectroscopy of 13CD3OD

We have used Fourier Transform spectral data on the C-O stretching mode of ¹³CD₃OD in order to perform a vibro-rotational analysis for this molecule. We have estimated a few molecular parameters of the ground and C-O stretching vibrational modes. Based on these parameters, and by using the Kwan-Dennison model, we propose assignments for a number of far-infrared laser transitions of ¹³CD₃OD.