Calculated ro-vibrational spectrum of 7Li+3 and 7Li2 6Li+

Calculated ro-vibrational energy levels (J ⩽ 4) and transition intensities are presented for the two most abundant isotopomers of Li⁺₃. The calculations use the recent ab initio potential energy surface of Searles et al. (Spectrochim. Acta 43A, 699 (1987); 44A, 505 (1988); 44A, 985 (1988)). The rotational levels of the ground state and vibrational fundamentals are given in terms of parameterised Hamiltonians due to Watson retaining terms to fourth-order. The small splitting of the degenerate ν₂ mode in the mixed isotopomer leads to strong Coriolis coupling between the ν₂ and ν₃ in ⁷Li₂ ⁶Li⁺.     

Isotope effects in the relaxation of6Li and7Li nuclei in paramagnetic aqueous solutions

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, p. 2429, October, 1988.     

6/7Li NMR study of the Li1-zNi1+zO2 phases

A series of Li1-zNi1+zO2 materials have been synthesised by the coprecipitation route. An X-ray diffraction study was carried out on these materials using the Rietveld method to determine the departure from the ideal stoichiometry z, which ranges from 0 to 0.138. The actual Li/Ni ratio was also checked by chemical analyses using inductively coupled plasma (ICP) for each sample. The stoichiometric sample (z approximately 0) was obtained using a 15% Li excess. (6/7)Li NMR results from LiNiO2 (z approximately 0) show that the asymmetric shape of the NMR signal is due to anisotropy. Calculations give evidence that the paramagnetic dipolar interaction from the electron spins carried by Ni is anisotropic but does not completely explain the experimental anisotropy. (6)Li MAS NMR (magic angle spinning NMR) experiments and temperature standardisation NMR measurements unambiguously assign the isotropic position at +726 ppm. The static-echo NMR spectra of the non-stoichiometric Li1-zNi1+zO2 phases also exhibit an asymmetric shape whose width increases with the departure from the ideal stoichiometry z. (6/7)Li static and MAS NMR show that the 2zNi(2+) ions thus formed modify the dipolar interaction within the materials and also affect the Fermi contact interaction, since a distribution of Li environments is observed using (6)Li NMR for non-stoichiometric samples.     

Theory of laser enhancement of ultracold reactions: the fermion-boson population transfer by adiabatic passage of 6Li+6Li7Li(Tr=1 mK)-->6Li6Li+7Li(Tp=1 mK)

We present a new theory of population transfer by adiabatic passage. This theory relates laser catalysis to adiabatic passage, enhancing chemical reactions with the freedom to choose the translational energies of the reactants and products separately. The process, A+BC<-->(Planck's over omega(p) )ABC*(v)<-->(Planck's over omega(s))AB+C, involves two laser fields that are slowly varying so the process is adiabatic, and sufficiently intense so the population of the intermediate bound complex (ABC) is minimized. We apply this theory to the collinear exchange reaction (6)Li+(7)Li(2)(T(r))<-->(Planck's over omega(p))((6)Li(7)Li(7)Li)*<-->(variant Planck's over 2piomega(s) ) (6)Li(7)Li(T(p))+(7)Li. We show that at translational energies T(p)=T(r)=1 mK with a narrow energy bandwidth of delta(E)=0.01 mK, we can obtain nearly total (> or =98%) population transfer from the reactant to the product states. This can be done with a pump laser and a Stokes laser in an "intuitive" sequence (t(p)相似文献   

Theory of laser enhancement and suppression of cold reactions: the fermion-boson 6Li+7Li2<-->(variant Planck's over 2pi omega0) 6Li7Li+7Li radiative collision

We present a nonperturbative time-dependent quantum mechanical theory of the laser catalysis and control of a bifurcating A+BC<-->(variant Planck's over 2pi omega(0))ABC*(v)<-->(variant Planck's over 2pi omega(0) )AB+C reaction, with ABC*(v) denoting an intermediate, electronically excited, complex of ABC in the vth vibrational state. We apply this theory to the low collision energy fermion-boson light-induced exchange reaction, (6)Li((2)S)+(7)Li(2)((3)Sigma(u)(+))<-->(variant Planck's over 2pi omega(0))((6)Li(7)Li(7)Li)*<-->(variant Planck's over 2pi omega(0))(6)Li(7)Li((3)Sigma(+))+(7)Li((2)S). We show that at very low collision energies and energetically narrow (approximately 0.01 cm(-1)) initial reactant wave packets, it is possible to tune the yield of the exchange reaction from 0 to near-unity (yield >or=99%) values. Controllability is somewhat reduced at collisions involving energetically wider (approximately 1 cm(-1)) initial reactant wave packets. At these energetic bandwidths, the radiative reactive control, although still impressive, is limited to the 0%-76% reactive-probabilities range.     

Ta 5+掺杂Li7La3Zr2O12的合成及其性能研究

本文采用固相法制备了Ta ⁵⁺掺杂的石榴石型无机固体电解质Li_7-xLa₃Zr_2-xO₁₂（xTa-LLZO）,研究了不同的掺杂量对材料性能的影响. 通过X射线发射光谱（XRD）、冷场发射电子扫描电镜（FESEM）和电化学阻抗（EIS）对材料进行物理表征和阻抗测试,并且组装LiFePO₄//LLZTO//Li全固态锂电池测试电池的循环稳定性. 结果表明,随着Ta ⁵⁺掺杂的增加,材料呈现出一个单一的立方相结构,当Ta ⁵⁺掺杂量为14.09wt.%（即x=0.3）时,材料的室温离子电导率达到最大（2.58×10 ^-4 S·cm ^-1）,呈现出稳定的立方相结构且具有相对较高的致密度（89.16%）,并具有较稳定的循环稳定性,经过50个循环后容量保持率依然保持到88.67%左右.     

Stereocontrolled synthesis of (5+5), (5+6) and (6+6) 3-spiropseudonucleosides

3-Spiropseudonucleosides, in which the heterocyclic base is a five-membered (oxazolidine, imidazolidine, thiohydantoin) or six-membered (perhydrooxazine) heterocycle, have been prepared starting from a hexofuranos-3-ulose. The method leads to good yields and is completely stereoselective. The key intermediate is a sugar iso(thio)cyanate.     

Synthesis,Structural Characterization,and Cation Transport of Tripotassium Pentabismuth Arsenate K3Bi5(AsO4)6

During the exploration of the K₂O-Bi₂O ₃ -As₂O₅ system, single crystals of a new arsenate of trivalent bismuth, K₃Bi₅(AsO₄) ₆, were isolated by solid state reaction at 600°C. The title compound crystallizes in the monoclinic system, space group C2/c (N°15) with a = 18.257(2) Å, b = 7.260(1) Å, c = 20.130(4) Å, β = 119.86(1)°, and Z = 4. Its structure consists of a three-dimensional framework made up of AsO₄ tetrahedra and BiO₆ and BiO₇ polyhedra sharing edges and corners, delimiting cavities wherein K⁺ ions reside. This compound exhibits a potassium ion conductivity but with rather low conductivity value.     

生物铵转运蛋白对NH3/NH4+作用机理研究

铵转运蛋白广泛存在于细菌、真菌、植物以及动物等各种生命体中。生物铵转运蛋白对NH₃/NH₄⁺的传输作用已被广泛研究,然而,对于通过铵转运蛋白疏水性孔腔的物种是带电荷的NH₄⁺离子还是电中性的NH₃分子,仍存在很大争议。本文综述了近年来生物铵转运蛋白对NH₃/NH₄⁺作用机理的研究进展,主要包括NH₃或NH₄⁺的传输及NH₃和H⁺共传输等机理。     

IPr3Si3Cl5+: A Highly Reactive Cation with Silanide Character

The reaction of a metastable SiCl₂ solution with the sterically less‐demanding carbene N,N‐diisopropylimidazo‐2‐ylidene (IPr) yields the salt [(IPr₃Si₃Cl₅)⁺]Cl^? ( 1 ‐Cl), containing a silyl cation with a Si₃ backbone. Salt 1 is highly reactive, but it can be used as a reagent in deuterated dichloromethane, whereby dehalogenation with Me₃SiOTf (OTf=O₃SCF₃) gives the dicationic silyl halide [(IPr₃Si₃Cl₄)]²⁺ 2 . Quantum chemical calculations show that the HOMO is localized at the negatively charged central silicon atom of 1 and 2 , and thus although both compounds are cations they are better described as silanides, which was also corroborated by NMR investigations.     

Regulating Cation Interactions for Zero-Strain and High-Voltage P2-type Na2/3Li1/6Co1/6Mn2/3O2 Layered Oxide Cathodes of Sodium-Ion Batteries

Deep sodium extraction/insertion of sodium cathodes usually causes undesired Jahn–Teller distortion and phase transition, both of which will reduce structural stability and lead to poor long-cycle reliability. Here we report a zero-strain P2- Na_2/3Li_1/6Co_1/6Mn_2/3O₂ cathode, in which the lithium/cobalt substitution contributes to reinforcing the host structure by reducing the Mn³⁺/Mn⁴⁺ redox, mitigating the Jahn–Teller distortion, and minimizing the lattice change. 94.5 % of Na⁺ in the unit structure can be reversibly cycled with a charge cut-off voltage of 4.5 V (vs. Na⁺/Na). Impressively, a solid-solution reaction without phase transitions is realized upon deep sodium (de)intercalation, which poses a minimal volume deviation of 0.53 %. It attains a high discharge capacity of 178 mAh g⁻¹, a high energy density of 534 Wh kg⁻¹, and excellent capacity retention of 95.8 % at 1 C after 250 cycles.     

Vibrational spectra of 6Li/7Li and H/D substituted single crystal lithium sulfate monohydrate

Infrared and Raman spectra of several isotopic species of Li₂SO₄·H₂O were investigated. Bands with a lithium-isotopic shift of 3–8% were observed in the spectral region from 300–580 cm⁻¹. The spectra of the deuterated single crystals indicate a coupling between the lithium vibrations and the librational modes of the water molecules. The assignment of the bands with appreciable ⁶Li/⁷Li isotope effect to translational modes of the lithium atoms is confirmed by a rough normal coordinate calculation.     

Electric Properties of Solid Solutions in the Systems Li6MoN4−Li7NbN4 and Li6WN4−Li7TaN4

The phase balance and electric properties of products in the systems Li₆MoN₄–Li₇NbN₄ and Li₆WN₄–Li₇TaN₄ are studied. It is shown that continuous series of solid solutions whose lithium-cation conductance decreases during mutual doping exist in either system. The activation energies for the long- and short-range motion of lithium charge carriers, determined from the electroconductance and ⁷Li NMR data, equal 55 and 46 or 25 and 14 kJ mol^–1 for the initial compounds of the first and second systems, respectively. The difference that large is attributed to a large contribution of the coulombic correlation for the hops of lithium charge carriers in both systems. Basic parameters of the correlation (time, distance, relaxation time) are calculated from experimental data. The strong correlation in the systems is presumed to stem from a weak screening of the coulombic field in the nitrides, rather than from a high concentration of charge carriers.     

Lithium vanadate Li3+xV6O13 at low temperature

The structure of Li_3+xV₆O₁₃ [x = 0.24 (3)] at 95 K has been solved and refined using single‐crystal X‐ray diffraction. The refined lithium content corresponds to two fully occupied Li sites and one partially occupied Li site. A doubling of the c axis is observed upon cooling from room temperature, and this change is associated with shifts of the V atoms. The resulting space group is C2/c. The Li disorder present in the Li₃V₆O₁₃ phase at room temperature is also observed in the low‐temperature phase reported here.     

Studies of EPR parameters for Mn5+ -doped Li3PO4 and Li3VO4 crystals

The EPR parameters (zero-field splitting D and g factors g parallel, g perpendicular) of Mn5+ -doped Li3PO4 and Li3VO4 crystals are calculated from the complete high-order perturbation formulas based on a molecular orbital scheme for a 3d2 ion in tetragonal MX4 clusters. These formulas include not only the contribution coming from crystal-field excitations, but also that arising from charge-transfer excitations (which is discarded in crystal field theory). The calculated results are in reasonable agreement with the observed values. The contributions to EPR parameters coming from the charge-transfer excitations are comparable with those arising from the crystal-field excitations. It appears that for a high valence state 3dn ion in crystals, the reasonable explanations of EPR parameters should take the contributions due to both crystal-field and charge-transfer excitations into account.