Infrared Spectra and Theoretical Calculations of BS2 and BS2-： Strong Pseudo Jahn-Teller Effect

Laser ablated boron atoms have been reacted with hydrogen sulfide and the reaction products condensed with argon at 4 K, which gave BS2, BS2-, HSBS, and HBS molecules. Reagent isotopic substitution （H2S, H234S, D2S, 10 B, 11B） and variation of boron and hydrogen sulfide concentrations have been used to identify the major products. Both BS2-- and BS2 were identified as linear molecules with no significant difference in the structure parameters, but the B-S anti-symmetric stretching vibration of BS2 is significantly lower than that of BS2-, which is ascribed to pseudo Jahn-Teller effect. Theoretical calculation was employed to have an insight into the interaction nature of the bonds in the corresponding products.

Pseudo Jahn-Teller Effect in Puckering and Planarization of Heterocyclic Compounds

The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all the papers devoted to this problem, it is shown that the instability of planar configurations of heterocyclic molecules leading to symmetry breaking and distortions is induced by the pseudo Jahn-Teller effect (PJTE). Special attention in this work is paid to the mechanism of suppression and enhancement of the PJTE distortions of heterocycles by oxidation, reduction, and chemical substitutions. It is demonstrated that oxidation of 1,4-dithiine containing compounds leads to suppression of the PJTE and to restoration of their planar nuclear configurations. An example of a dibenzo[1,2]dithiine molecule is used to demonstrate the mechanism of enhancement of the PJTE by reduction. It is shown that the reduction of the neutral C12H8S2 molecule up to the dianion (C12H8S2)2- enhances the PJTE, followed by the S-S bond cleavage and significant structural distortions of the system. The change of the PJTE by chemical substitutions, accompanied either by puckering or by planarization of heterocyclic compounds, is discussed using as examples 1,4-ditinine and its S-oxygenated derivatives.

Ultrasonic Study on Jahn-Teller Distortions in La1/3Sr2/3CoO3

The longitudinal ultrasonic velocity （V1）, attenuation （α1）, magnetization and resistivity of single phase polycrystalline La1/3Sr2/3CoO3 were measured as a function of temperature from 20 K to 300 K. The resistivity shows metallic behavior in the whole temperature range and a kink at 235 K was observed, which coincides with the ferromagnetic transition temperature （Tc）. As the temperature cools down from Tc, the V1 softens conspicuously at beginning and reaches a minimum at 120 K. After that the V1 dramatically stiffens below 120 K accompanied by a wide attenuation peak. The analysis of the results suggests that these ultrasonic anomalies ;nay correspond to local lattice distortions via the Jahn-Teller effect of intermediate spin Co^3＋.

Discovering Cathodic Biocompatibility for Aqueous Zn–MnO_(2) Battery:An Integrating Biomass Carbon Strategy

Developing high-performance aqueous Zn-ion batteries from sustainable biomass becomes increasingly vital for large-scale energy storage in the foreseeable future.Therefore,γ-MnO_(2) uniformly loaded on N-doped carbon derived from grapefruit peel is successfully fabricated in this work,and particularly the composite cathode with carbon carrier quality percentage of 20 wt%delivers the specific capacity of 391.2 mAh g^(−1)at 0.1 A g^(−1),outstanding cyclic stability of 92.17%after 3000 cycles at 5 A g^(−1),and remarkable energy density of 553.12 Wh kg^(−1) together with superior coulombic efficiency of~100%.Additionally,the cathodic biosafety is further explored specifically through in vitro cell toxicity experiments,which verifies its tremendous potential in the application of clinical medicine.Besides,Zinc ion energy storage mechanism of the cathode is mainly discussed from the aspects of Jahn–Teller effect and Mn domains distribution combined with theoretical analysis and experimental data.Thus,a novel perspective of the conversion from biomass waste to biocompatible Mn-based cathode is successfully developed.

High-Temperature Superconductivity—An Electron Transfer Phenomenon

The increase of the critical temperature Tc for superconductivity in Al1−x(SiO2)x cermets with increasing x correlates with a decrease of the electron density n due to electron transfer, expressed by Tc/Tc,max=1−γ⋅n2(*). Behind the formula (*) and Tc/Tc,max=1−82.6(P−0.16)2, which is characteristic of hole-doped cuprat high-temperature superconductors, lies a general phenomenon, namely electron transfer, which equalizes potential differences in the material and leads to a strong reduction of n. P is the fraction of holes filled by the transferred electrons. A quantitative consideration gives Tc(x)/Tc,max=1−(1−x1−x0)2(**), where x is the doping concentration and x0 is the concentration at which superconductivity begins. At x=xmax=1the electron source is completely depleted and with further growth of x the hole density p starts to increase and Tc decreases until superconductivity disappears completely at x=2−x0. Taking into account the formula (**), the hypothesis arose that for x>xmaxTc/Tc,max=1−γ⋅p2(***), an analogue of the formula (*), and that superconductivity is possible not only by electron-Cooper pairs but also by paired holes. The mechanisms described here for HTSC suggest an analogy to the physics of semiconductors and that of nanocomposites: Electron-hole duality. The “P=1/8” anomaly in YBa2Cu3O6+x is caused by the simultaneous presence of electrons and holes, a consequence of incomplete electron transfer.

固相分段法制备锂离子电池正极材料LiMn_2O_4的实验

通过L25(55)拉丁正交实验,利用极差分析法对制备LiMn2O4的反应条件进行优化,找出了合成LiMn2O4的合适工艺. 固相分段法制备LiMn2O4的过程中,氧化物的合成反应温度、氧气流量、LiOH的分解反应温度、锂锰摩尔比及恒温时间依次为主要影响因素. LiMn2O4实验电池的电化学测试表明,3 V左右放电平台可达8 h,初始放电比容量为140 mAh/g左右. 从结构化学角度分析了尖晶石型锰酸锂材料的充放电过程和产生Jahn-Teller效应的原因.

Insights into Ti doping for stabilizing the Na_(2/3)Fe_(1/3)Mn_(2/3)O_(2)cathode in sodium ion battery

Iron-and manganese-based layered metal oxides,as cathodes for sodium ion batteries,have received widespread attention because of the low cost and high specific capacity.However,the Jahn-teller effect of Mn^(3+)ions and the resulted unstable structure usually lead to continuously capacity decay.Herein,Titanium(Ti)has been successfully doped into Na_(2/3)Fe_(2/3)Mn_(2/3)O_(2)to suppress the Jahn-Teller distortion and improve both cycling and rate performance of sodium ion batteries.In situ high-energy synchrotron X-ray diffraction study shows that Ti-doped compound(Na_(2/3)Fe_(1/3)Mn_(0.57)Ti_(0.1)O_(2))can maintain the single P2 phase without any phase transition during the whole charging/discharging process.Various electrochemical characterizations are also applied to explore the better kinetics of sodium ions transfer in the Na_(2/3)Fe_(1/3)Mn_(0.5)7 Ti_(0.1)O_(2).This work provides a comprehensive insight into the Ti-doping effects on the performance from both structural and electro kinetic perspectives.

Jahn-Teller distortion assisted interstitial nitrogen engineering:Enhanced oxygen dehydrogenation activity of N-doped Mn_(x)Co_(3-x)O_(4) hierarchical micro-nano particles

Rational design of earth-abundant transition metal oxides catalysts is highly desirable for developing sustainable chemical processes.Herein,we demonstrate a prospective interstitial nitrogen engineering for fabricating oxygen vacancies(OVs)-rich nitrogen-doped-Mn_(x)Co_(3-x)O_(4)(N-Mn_(x)Co_(3-x)O_(4))oxide catalyst,in which the ratio of OVs concentration of N-Mn_(x)Co_(3-x)O_(4)to Mn species is as high as 1:1,according to the characterizations of X-ray absorption(XAS)and X-ray photoelectron(XPS)spectroscopies.The promising strategy of interstitial nitrogen engineering through lattice distortion caused by the Jahn-Teller effect can significantly increase the amount of interstitial nitrogen.The resulting catalyst enables an additive-free aerobic dehydrogenation coupling of aromatic amine to afford azo compounds with>99%yield and>99%selectivity at 60☆.We observed the superb catalytic activity is promoted by the enhanced oxygen mobility in OVs,which were created by the interstitial nitrogen in the catalyst matrix.The presence of interstitial nitrogen in transition metal oxides in this study shows how the manipulation of catalyst matrix can increase the OV sites to promote aerobic oxidation reaction.

Infrared Spectra of La_(0.65)Ba_xMnO_(3-δ) Oxides

The infrared spectra of La_(0.65)Ba_xMnO_(3-|?￡(c) (x = 0.35, 0.33 and 0.30) were investigated experimentally. The result shows that the sample La_(0.65)Ba_xMnO_(3-|?￡(c) has the largest Curie temperature and the smallest resistivity and wave number of the stretching vibration mode of MnO_6 octaheUron at 300 K among the investigated samples. However, the absorption strength for the stretching vibration mode of Mn0_6 octahedron in La_(0.65)Ba_xMnO_(3-|?￡(c) is stronger for parainagnetic phase than that for ferromagnelic phase, which may be connected with the reducing of the dynamic in- coherent Jahn-Teller distortion below Curie temperature. In addition, the large shift of wave number for the stretching mode at the temperatures from 293 to 423 K has been observed in La_(0.65)Ba_xMnO_(3-|?￡(c), which may be due to the in- crease of the Mn-O bond length with temperature increasing.

Characterization and photoluminescence properties of ultrafine copper molybdate(α-CuMoO_4) powders prepared via a combustion-like process

We report a simple method for preparing copper（II） molybdate（CuMoO_4） powders via a combustion-like process. A gel was first prepared by the polymerizable complex method, where citric acid was used as a complexing and polymerizing agent and nitric acid was used as an oxidizing agent. The thermal decomposition behavior of the（CuMo）-precursor gel was studied by thermogravimetry–differential thermal analysis（TG–DTA）, Fourier transform infrared spectroscopy（FTIR）, and X-ray diffraction（XRD）. We observed that the crystallization of CuMoO_4 powder was completed at 450°C. The obtained homogeneous powder was composed of grains with sizes in the range from 150 to 500 nm and exhibited a specific surface area of approximately 5 m^2/g. The average grain size increased with increasing annealing temperature. The as-prepared CuMoO_4 crystals showed a strong green photoluminescence emission at room temperature under excitation at 290 nm, which we mainly interpreted on the basis of the Jahn-Teller effect on [MoO_4^（2-）] complex anions. We also observed that the photoluminescence intensity increased with increasing crystallite size.

Cu-substitution P2-Na_(0.66)Mn_(1-x)Cu_(x)O_(2) sodium-ion cathode with enhanced interlayer stability

P2-type Mn-based layered oxides are viewed as promising cathode materials for sodium ion battery by virtue of their high theoretical capacity.Considering that pure Na_(2/3)MnO_(2)suffers from poor cycling performances,Cu-substitution strategy is proposed to effectively alleviate this issue.However,the structural evolution mechanism of the Cu-containing samples still remains unclear.Herein,we propose that CuSubstitution P2-type Na_(0.66)Mn_(1-x)Cu_(x)O_(2)with enlarged lattice parameters are conducive to improving the interlayer structure stability through mitigating TMO_(2)slabs distortion.Proved by synchrotron XAS spectra and ex/in situ XRD,the expansion/contraction of MnO_6 octahedron is dramatically reduced with the increased Cu content,showing the facilitated Na ion diffusion.Furthermore,when the ratio of Cu to Mn reaches 1:4,the phase transition from P2 to P'2 type at the end of discharge can be suppressed,resulting in the improved interlayer skeleton stability.The Cu-containing samples with stable interlayer structure exhibit high capacity retention and outstanding rate performances(a capacity of 79.9 m Ah g^(-1)at 5C).This Cu-substitution strategy provides a promising approach to designing highly stable cathodes.

DFT Study on Structural Distortion and Vibronic Coupling of Vanadyl Porphyrin Anion and Cation

The geometries of one-electron reduced/oxidized species （[TOP]-/[VOP] ＋） of vanadyl por- phyrin （VOP） have been calculated with PBE1PBE method. The results show that for both [VOP]- and [VOP]＋ the ground states are triplet, in which one of the two unpaired electron occupies the dxy orbital of the V atom while the other occupies the n-orbital of porphyrin ring. Thus both [VOP]- and [VOP]＋ can be considered as n-radicals. The ground state of neutral VOP molecule is doublet with the unpaired electron occupying dxy orbital of V atom. In contract to the C4v symmetry of neutral VOP molecule, [VOP]- anion has a ＂rectangular＂ distorted C2v structure due to Jahn-Teller effect. The linear vibronic coupling constants for the Jahn-Teller active modes of [TOP]- were evaluated and the node patterns of frontier KS orbitals are used to explain the reason why the distortion occurs along specific modes. The ground state [VOP]＋ has a porphyrin ring with pronounced bond length alternation due to pseudo-Jahn-Teller effect, causing its symmetry declined from C4v to Ca. The bond length alternation is well explained with the node patterns of re-constructed frontier KS orbitals.

A Manganese Ions Ground State in Mn_xSi_1–x: Negative- <i>U</i>Properties Centre?

In the paper, the properties of magnetic diluted and strong correlated systems of MnxSi1–x systems are discussed. The double defects including manganese ion and silicon vacancy are the frame work of the our model introduced for the description of these systems properties. The role of the Jahn-Teller distortions of different symmetry types in MnSi system magnetic-properties formation is discussed. It has been established that the manganese related defect is the center with negative-U properties and Jahn-Teller’s full symmetric vibration mode initiates change of a crystal-field value from intermediate to strong.

Elastic Moduli in Cadmium Selenide Doped with Chromium

Temperature dependence of elastic moduli , , and the latter for the piezo-active and non-piezo-active versions, have been measured in the interval of 4 - 180 K at 28 - 262 MHz in a CdSe: Cr2+ crystal. Anomalies below 40 K have been found for all the moduli, except . The interpretation of the results has been carried out involving the Jahn-Teller effect and relaxation between the equivalent distortions of the tetrahedral CrSe4 centers.

High-excited-state splitting and multimode vibrational coupling in Mn^(4+)-activated fluoride phosphor

Excited-states play a crucial role in the optical absorption and luminescence of solids and hence their accurate information is highly desired. Herein, we attempt to seize the excited-states information of Mn^(4+)ions in K_(2)SiF_(6) microcrystals via measuring and calculating their variable-temperature photoluminescence excitation(PLE) spectra. At cryogenic temperatures, an unpredicted splitting of the high-excited-state is observed. Moreover, the two-split high-excited-state levels are further revealed to primarily couple with the two hyperfine split modes of quasi-localized ν2 vibration in the distorted Mn-F_(6) octahedral configuration,whereas the coupling strengths are found to be substantially different from each other. The slightly split vibrational mode is firmly supported by the low-temperature Raman spectra. Jahn-Teller lattice distortion is believed to be responsible for the observed splitting of the electronic high-excited-state and the quasi-localized vibrational mode.

Metal-metal bonds in Zintl clusters:Synthesis,structure and bonding in[Fe_(2)Sn_(4)Bi_(8)]^(3-)and[Cr_(2)Sb_(12)]^(3-)

We report here the synthesis and characterization of two new members of the M2 E 12 family of endohe-dral Zintl clusters,[Fe_(2)Sn_(4)Bi_(8)]^(3-)and[Cr_(2)Sb_(12)]^(3-),both of which contain open-shell metal dimers encap-sulated inside a triple-decker cluster of main-group atoms.The 75-electron[Fe_(2)Sn_(4)Bi_(8)]^(3-)cluster has a D4h-symmetric structure,while[Cr_(2)Sb_(12)]^(3-),despite having the same 75-electron count,is strongly dis-torted to a geometry that resembles a CrSb_(8)crown capped by a CrSb_(4)unit.The structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transi-tion metal,which leads,ultimately,to different electronic configurations in the two clusters.The trends precisely mirror those observed in the ME_(10)and ME_(12)families containing a single transition metal ion.

The growth mechanism of hydrotalcite crystal

From the point of growth units, the growth mechanism of hydrotalcite (HT) crystal is investigated in this paper. Results show that the growth morphology of HT is consistent with the model of anion coordination polyhedron growth units. The Raman shift of growth solutions of HT, Cu-HTlc, and Cu-Zn-HTlc are monitored using Raman spectroscopy. In the experiment, the growth units of Mg-Al-hydrotalcite are [Mg-(OH)6]4- and [Al-(OH)6]3-, and the growth units of Cu-Htlc and Cu-Zn-HTlc are [Mg-(OH)6]4- and [Al-(OH)6]3-, respectively. The growth process of hydrotalcite is as follows: growth units first incorpo- rate into metal layers, then metal layers adsorb An- and H2O, and the growth units incorporate into layer compounds according to this rule. Growth units will have different incorporations and growth morphologies caused by different growth surroundings. Furthermore, the reason why Cu-HTlc is difficult to synthesize is also interpreted in this paper.

Active site synergy of the mixed-phase cobalt diselenides with slight lattice distortion for highly reversible and stable lithium oxygen batteries

Many non-precious metal-based catalysts with high intrinsic activity for catalytic reactions are prone to structural degradation in practical application,which leads to poor stability.In this work,we propose c-CoSe_(2)/o-CoSe_(2)as the oxygen electrode of lithium-oxygen batteries(LOBs)to improve its cycle stability.The heterogeneous interface inside c-CoSe_(2)/o-CoSe_(2)leads to an increase in the covalence bonds between Co and Se ions,which greatly enhances the robustness of the crystal lattice,thereby improving the stability of the catalyst.In addition,the strong interaction between the mixed phases is favorable for adjusting the electron density around the active sites and boosting oxygen electrode kinetics.Moreover,the epitaxial growth of o-CoSe_(2)on c-CoSe_(2)will cause abundant heterogeneous interfaces and slight lattice distortion along the interfaces,thereby providing sufficient catalytic reaction sites.The DFT calculation results show that the optimized adsorption of intermediates at the heterogeneous interface plays an important role in boosting oxygen electrode reactions and improving the electrochemical performance of LOBs.The experimental results show that LOBs with the c-CoSe_(2)/o-CoSe_(2)electrodes exhibit outstanding performance,including large specific capacity of about 23,878 m A h g^(-1),high coulombic efficiency of up to 93.66%,and excellent stability of over 176 cycles(1410 h).

Roles of Electron Hopping on Orbital Ordering for Vanadium Spinels

We investigate the orbitM ordering quantitatively for the spinel systems RV204 （R=Mg, Zn, Cd） in the viewpoint of single-ion physics through the method of diagonalization. Through the quantitative calculation, it is found that the spin-orbit （SO）coupling and the Jahn-Teller （JT） effect enable the orbital ordering under the conditions of negligible electron hopping among different V3＋ sites. For the systems RV204, the electron hopping is implied to be observable from the energy gap in conductivity, so the orbital ordering of RV2 04 cannot be induced by the SO coupling and JT effect at definite temperature, which is on contrary to the conclusions in [Phys. Rev. Lett. 93 （2004） 157206].

Solvothermal Synthesis and Crystal Structures of Two Manganese Complexes [Mn（Ⅱ）（acac-）2（4,4＇-bipy）]n （bipy-4,4＇-bipyridine） and [Mn（Ⅲ）（acac-）3].4CO（NH2）2

Two special manganese complexes [Mn（II）（acac ）2（4,4＇-bipy）]n （bipy=4,4＇-bipyridine） （complex 1） and [Mn（II1）（acac-）3].4CO（NH2）2 （acacH=acetylacetone） （complex 2） were synthesized in the same strategy by sol- vothermal method. Single crystal X-ray diffraction revealed the complex 1 consists of one-dimensional infinite coordination chain, with the manganese centers bridged by 4,4＇-bipy. And free carbamides of complex 2 connect with each other through the hydrogen bonds to form a 14-membered carbamide ring and a zig-zag plane. Both enantiomers of Mn（III）（acac ）3 exist in the structure, forming a racemate. Furthermore, these enantiomers and those zig-zag planes are linked with hydrogen bonds to form an unique spatial network.