Theoretical study on the lithium bond interaction of furan homologues C4H4Y （Y=O,S） with LiCH3 via DFT and MP2

The optimizations geometries and interaction energy corrected by BSSE of the complexes between C4H4Y （Y=O, S） and CHiLi have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three complexes were obtained. Abnormally, the calculations showed that all the C10--Li14 bond lengths increased obviously but the blue-shift of C10-Li14 stretching frequency occurred after formed complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy corrections of complexes I-III is -45.757, -35.700 and -39.107 kJ·mol^-1, respectively. The analyses on the combining interaction with the atom-in-molecules theory （AIM） also showed that a relatively strong lithium bond interaction presented in furan homologues C4H4Y-LiCH3 systems. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the complex I is formed with n-σ type lithium bond interaction between C4H40 and LiCH3, complex II is formed with TT-s type lithium bond interaction between C4H4O and LiCH3, and complex III is formed with TT-s and n-s type lithium bond interactions between C4H4S and LiCH3, respectively.     

Formation, structure and properties of GeCn± and Ge2Cn± binary clusters

The binary cluster ions Ge₂C_n⁺/Ge₂C_n^- and GeC_n⁺ have been produced by laser ablation. The parity effect is present in the negative ions Ge₂C_n^-, though it is not very prominent. While the experiments tell that the parity effect is totally not shown in the positive ions Ge₂C_n⁺. An extensive theoretical investigation on GeCn/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂Cn/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) has been carried out by density functional theory at B3LPY level. The calculation shows that the low-lying states of GeC_n/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂C_n/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) are linear structure with germanium atoms locating at terminals respectively. The electronic distributions, ionization potential (IP_ad), elec-tron affinity (EA) and increasing bonding energy reveal that the parity effect of neutral species is much stronger than that of ions, which is attributed to the valence π-electrons. It is explained that the differences between experiments and cal-culations are due to the kinetic factor in the formation of Ge₂C_n^±.     

Theoretical study of N(C)―H…H―B multi-dihydrogen bonds

The optimized geometries, frequencies and interaction energy corrected with basis set superposition error (BSSE) of the multi-dihydrogen bond complexes C₄H₄NH…BH₄^–. and CH≡CH…BH₄^–. have been calculated at both the B3LYP/6-311++G** and the MP2/6-311++G** levels. The calculations were per-formed to study the nature of the N―H…H3―B and C―H…H2―B red shift multi dihydrogen bond in complex C4H4NH…BH^–₄ and CH≡CH…BH4–. The BSSE-corrected multi-dihydrogen bond interaction en-ergy of complex I (C₄H₄NH…BH₄^–.) and complexⅡ(CH≡CH…BH₄^–.) is -76.62 and -33.79 kJ/mol (MP2/6- 311++G**), respectively. From the natural bond orbital（NBO）analysis, we detailedly discussed the orbital interactions, electron density transfers, rehybridizations and the essential of the correlative bond length changes in the two complexes. In addition, solvent effect on the geometric structures, vibration frequencies and interaction energy of the monomer and complexes was studied in detail. It is relevant to the relatively dielectric constants (ε).     

Crystal structure and negative thermal expansion of solid solution Lu<Subscript>2</Subscript>W<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>12</Subscript>

A new series of solid solutions Lu₂W_3−x Mo _x O₁₂ (0.5≤x≤2.5) were successfully synthesized by the solid-state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare-earth tungstates and molybdates are found to crystallize in the same orthorhombic structure with space group Pnca and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients (TEC) of Lu₂W_3−x Mo _x O₁₂ are determined as −20.0×10⁻⁶ K⁻¹ for x=0.5 and −16.1×10⁻⁶ K⁻¹ for x=2.5 but -18.6×10⁻⁶ and −16.9×10⁻⁶ K⁻¹ for unsubstituted Lu₂W₃O₁₂ and Lu₂Mo₃O₁₂ in the identical temperature range of 200 to 800°C. High-temperature X-ray diffraction (XRD) data and bond length analysis suggest that the difference between W-O and Mo-O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

High-pressure synthesis and properties of CeO2-ZrO2 solid solution

Using nanoparticles of CeO₂ and ZrO₂ prepared by the chemical precipitation method as starting materials, the singlephase cubic Ce_0.5Zr_0.5O₂ solid solution (cCe_0.5Zr_0.5O₂) has been synthesized under 3.1 GPa at 1073 K for the first time. The structure of the c-Ce_0.5Zr_0.5O₂ has not been changed before and after annealing at 773 K for 1 h. Only an unknown EPR signal (g =1.990) has been observed in the c-Ce_0.5Zr_0.5O₂ and not varied after annealing at 773 K for 1 h, which exhibited that there exists no Ce³⁺ in the c-Ce_0.5Zr_0.5O₂ and the Ce⁴⁺ has not been reduced into Ce³⁺ after annealing. The transport mechanism is ionic for the c-Ce_0.5Zr_0.5O₂. The bulk conductivity (σ =1.2 ×10⁻⁵ S/cm at 823 K, σ=2.1 × 10⁻³ S/cm at 1123 K) is the same as that of CeO₂, but smaller than that of Y₂O₃-stabilized ZrO₂. A marked curvature at T = 823 K has been observed in the Arrhenius plot of the bulk conductivity. The activation energy below 823 K is lower than that above 823 K, and the reason has been discussed.     

An in-situ DRIFTS study in the reaction between NO x and soot on BaAl2O4

The interactions between NO, O2 and their mixture on BaAl2O4, as well as the reaction of NOx with soot in the presence of O2, have been investigated using Diffuse Reflectance Infrared Fourier Transform Spectroscopy （DRIFTS）. NO adsorption produces only nitrites species in the absence of O2. NO2 adsorption produces nitrates species besides nitrites species. The produced nitrites will further react with O2, Osurf^-. and Olattice^2- to form nitrates. The reaction of NOx with soot begins with the reaction of nitrates with soot oxygenated complex （C（O））, which is regarded as the key and rate determining step. A reaction pathway is proposed for the catalyzed reaction of NOx with soot in the presence of O2.     

The comparative investigation on redox property and second-order nonlinear response of Keggin-type α-[PM12O39NPh]3− (M = W and Mo) and Mo6NPh

Keggin-type phenylimido-polyoxometalates α-[PM₁₂O₃₉NPh]³⁻ (M = W and Mo) have been systematically investigated on the electronic structures, redox as well as nonlinear optical (NLO) properties by density functional theory (DFT). The strong M≡N bond confirmed by natural bond orbital (NBO) analysis comprises one s bond and two π bonds, the same as Mo≡N in [Mo₆O₁₈NPh]²⁻. Furthermore, phenylimido segment effectively modifies the electronic properties of α-[PM₁₂O₃₉NPh]³⁻. On one hand, when enlarging the inorganic cluster from {Mo₆O₁₈} to {PMo₁₂O₃₉}, the energy gap between HOMO and LUMO in α-[PMo₁₂O₃₉NPh]³⁻ decreased, resulting in enormously anodic shift for the reduction potential, while the excitation energy is less and the total second-order polarizability β ₀ is up to 438-3×10⁻³⁰ esu, which is nearly 10 times larger than that of [Mo₆O₁₈NPh]²⁻. On the other hand, when metal W in α-[PM₁₂O₃₉NPh]³⁻ is substituted by Mo, the interaction between Mo and N is enhanced and the redox ability becomes stronger. The β ₀ value for α-[PMo₁₂O₃₉NPh]³⁻ is more than 5 times higher than that of α-[PW₁₂O₃₉NPh]³⁻. It indicates that changing appropriate metal or enlarging the inorganic cluster will improve the redox properties and second-order nonlinear response. Moreover, the electron transition for three compounds mentioned above occurred mainly from organoimido segment (as the electron donor) to polyanion cluster (as the acceptor). As a result, α-[PMo₁₂O₃₉NPh]³⁻ may be a promising candidate for oxidant and nonlinear optical material. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by National Natural Science Foundation of China (Grant No. 20573016), Training Fund of NENU’s Scientific Innovation Project (Grant No. NENUSTC07017), Science Foundation for Young Teachers of Northeast Normal University (Grant No. 20070304) and Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT)     

Investigation of the interfacial water structure on poly[2-（dimethylamino）ethyl methacrylate] at the air/water interface by sum frequency generation vibrational spectroscopy

The effect of pH on the conformation of surface alkyl groups and the structure of interfacial water molecules on poly[2-(dime-thylamino)ethyl methacrylate](PDEM) at the air/water interface were investigated with sum frequency generation vibrational spectroscopy(SFG-VS).At pH 4.1,the hydrogen bonding SFG spectra were similar to that of the air/pure water interface.As the pH increased from 5.4 to 9.6,the SFG intensities of both highly ordered hydrogen bonding(3200 cm-1 band) and less-ordered hydrogen bonding(3400 cm-1 band) were enhanced because of the charge-induced effect of deprotonated PDEM.The free OH peak disappeared completely because it was replaced by interfacial PDEM molecules.At pH 11.5,a new spectral band appeared at about 3580 cm-1 in the ppp and sps spectra,and this could be assigned to the C2v asymmetric stretching mode of the water molecules through molecular symmetry simulation.These hydrogen bonding structures are fully consistent with the conformational change of PDEM alkyl groups,and PDEM molecules act as a Hofmeister solvent.PDEM molecules are kosmotropic when they are charged and become more chaotropic as the pH increases.     

Lithium bond structures of HnY （n=2, 3; Y=O,S, N）…LiNH2 and the abnormal blue shift of N-Li bond

The optimized geometries of the complexes between HnY （n=2, 3; Y=O, S, N） and LiNH2 have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three stable complexes were obtained. Frequency analysis showed that the enlarged 2N-4Li presents the abnormal blue shift in three complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy （ZPE） corrections of complex Ⅰ-Ⅲ is -58.65, -31.66 and -69.59 kJ·mol^-1 （MP2）, respectively. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the H2O…LiNH2 （complex I） and H3N…LiNH2 （complex Ⅲ） are formed with coexisting σ-s and n-s type lithium bond interactions, complex Ⅱ is formed with ττ-s type lithium bond interaction between HnY （n=2,3; Y=O, N） and LiNH2, and H2S…LiNH2 （complex Ⅱ） is formed with n-s type lithium bond interaction between H2S and LiNH2. Natural resonance theory （NRT） and atom in molecule （AIM） theory have also been studied to investigate the bond order and topological properties of the lithium bond structures.     

Synthesis and crystal structure of new supramolecular adducts of [PtCl6]2− with cucurbit [7] uril: [(H3O)2 (PtCl6)]3 (C42H42N28O14)2·H2O

A novel supramolecular adduct [(H₃O)₂ (PtCl₆)]₃ (C₄₂H₄₂N₂₈O₁₄)₂·H₂O (1) was synthesized by mixing [PtCl₆]²⁻ and cucurbit [7] uril in solution of hydrochloric acid. The crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system and space group F dd2 with cell dimensions:a=4. 705 33 (5) nm,b=7. 153 80 (6) nm,c=1. 894 61 (2) nm,Z=16,V=63, 7744 (11) nm³,D _c =1.534 g/cm³, μ=3. 007 mm⁻¹,F(000)=29 120,R ₁=0.070 7,wR ₂=0. 169 2. In crystal, the cucurb [7] uril molecules from two zig-zag chains. Foundation item: Supported by the National Natural Science Foundation of China (20172040) Biography: Yan kun (1977-), female, Master, research direction: macrocyclic chemistry.     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.     

First-principles studies of the adsorption of O2 on Al （001）

Oxidationisaubiquitousphenomenonofnature.Theeconomiclossduetooxidationisverylargeeveryyear.Theinvestigationoftheadsorptionofoxygenonthesur-facesofmetalsisofgreatimportanceforbetterunder-standingoftheoxidationmechanismbecauseitistheverybeginningstageofoxidationofmetals.Itisgenerallybe-lievedthattheprocessofO2adsorptiononmetalsisinanorderofO2?O?O-?O2-,andthefollowingstagesareoxidenucleation,growthandtheoxidefilmformation.Astheprocessofadsorptionistooquicktobeobservedbyexperiments,atheoreticals…     

I-V andC-V properties of TiO2 thin film by pulsed-laser reactive deposition

TiO-2 thin films have bee deposited on p-Si(111) substrates by pulsed-laser ablation of metallic Ti target in the O-3 ambient. The current-voltage and capacitance-voltage of the Al/TiO-2/Si capacitors are measured. The results show that the dielectric constant of thin film after being annealed at 700℃ is found to be 46, and the border trap density and the interface state density at the TiO-2/p-Si interface are 1.8×10 12 cm -2 and 2×10 12 eV -1·cm -2, respectively. The conduction mechanisms of as-deposited films are also discussed.     

Preparation and kinetics of the thermal decomposition of nanosized CuC2O4−ZnC2O4·2H2O

The physical mixture of nanosized CuC₂O₄−ZnC₂O₄·2H₂O, as precursors of CuO−ZnO, have been prepared by the one-step solid state reaction method at room temperature. The thermal decomposition processes taking place in the solid state oxalate mixture of nanometer CuC₂O₄−ZnC₂O₄·2H₂O have been studied in static air using TG, DSC, XRD and TEM techniques. TEM showed that the grain size of the decomposition product is 5–15 nm. The values of the activation energyE _α were determined using the isoconversional procedure of KAS method and the Ozawa method. The most possible mechanism functionf(α) of the thermal decompositions of nanosized CuC₂O₄−ZnC₂O₄·2H₂O are defined using the comparative method, function models of the decomposition of CuC₂O₄ and ZnC₂O₄ follow the same mechanism function “Avrami-Erofeev equation”. The pre-exponential factorA is obtained on the basis ofE _α andf(α), thus the thermal analysis kinetic triplet of the decompositions of nanosized CuC₂O₄−ZnC₂O₄·2H₂O are determined. Foundation item: Supported by the key Natural Science Fund of Deparartment of Science and Technology of Hubei Province (2001ABA099). Biography: CHEN Donghua(1946-), male, Professor, research direction: material synthesize and thermal, analysis kinetics.     

Effects of Yb^3＋ codoping on visible and near infrared emissions of Er^3＋-Yb^3＋ codoped Al2O3 powders by the sol-gel method

The 0.1 mol% Er^3＋ and 0-2 mol% Yb^3＋ codoped Al2O3 powders were prepared by the sol-gel method, and the phase structure, including only two crystalline types of doped Al2O3 phase, γ-（Al,Er, Yb）2O3 and θ-（Al,Er, Yb）2O3, was detected at the sintering temperature of 1000℃. The visible and near infrared emissions properties depended strongly on the Yb^3＋ codoping, and the corresponding maximal peak intensities centered at about 523, 545, 660 and 1533 nm were obtained respectively for the 0.1 mol% Er^3＋ and 0.5 mol% Yb^3＋ codoped Al2O3 powders, which were composed of θ-（Al,Er,Yb）2O3 and a small amount of γ-（Al,Er, Yb）2O3 phases. The two-photon absorption process was responsible for the visible up-conversion emissions, and the one-photon absorption process was involved in the near infrared emissions of the Er^3＋-yb^3＋ codoped Al2O3 powders.     

Synthesis of layered LiMnO2 byin situ oxidation-intercalation and a study of the reaction mechanism and electrochemical performance

Using Mn(OH)₂ as precursor, LiOH as lithiating agent and (NH₄)₂S₂O₈ as oxidant, layeredo-LiMnO₂ was obtained by a novel method—in situ oxidation-intercalation under mild conditions (80 °C). The product was characterized by XRD, ICP, TEM and⁷Li-NMR. The results reveal that orthorhombic LiMnO₂ with high purity and good crystallinity can be obtained by this method. During electrochemical tests, a LiMnO₂/Li cell shows an initial reversible capacity of 208 mAh · g⁻¹ and a reversible capacity of 180 mAh · g⁻¹ after 30 cycles at room temperature.     

Changes of photosynthetic capacity of some plant species under very high CO2 concentrations in Biosphere 2

Conclusions The initial slope of A/ light curve became steep under high CO₂ (700 μmol · mol^-1) compared with that under low CO₂ (350 μmol · mol^-1) for the C₃ species growing in very high CO₂(>2 200 μmol · mol^-1) for a long period. The light compensation points remained unchanged, but the light saturation points were found increased. The ϕ_m,_app and A_max of the C₃ species increased respectively by 79 % and 80 %, while those of C₄ species decreased by 10% and 14%, respectively. The shape of A/light curve of C₄ species did not change. Such results indicated that C₃ species increased the capacity of photosynthesis, while C₄ did not change, otherwise it decreased a little. This work only compared the changes of capacity in photosynthesis of some species under different CO₂ levels in Biosphere 2. We need further investigation on the effects of high CO₂ on the same species outside Biosphere 2, in order to fully undertand the effects and mechanism of response of plants to the elevated CO₂.