H2在Al7-团簇解离吸附的理论研究

利用高精度从头计算方法研究了H₂分子在Al₇^-阴离子团簇上的吸附及解离过程, 确定了分子吸附及解离吸附的稳定结构,并分析了各结构的光电子能谱. 计算表明H₂在Al₇^-上为弱的物理吸附,吸附能约为0.02 eV;解离过程的能垒约为0.75 eV. 对团簇及解离吸附结构的态密度与实验得到的光电子能谱的比较表明二者能够很好地符合, 确定H₂与激光烧蚀产生的团簇直接反应时能在Al₇^-上发生解离. 关键词： 7^-')" href="#">Al₇^- 2')" href="#">H₂ 解离吸附 从头计算     

Luminescent characteristics of LiCaBo3:M (M=Eu, Sm, Tb, Ce, Dy) phosphor for white LED

LiCaBO₃:M (M=Eu³⁺, Sm³⁺, Tb³⁺, Ce³⁺, Dy³⁺) phosphors were synthesized by a normal solid-state reaction using CaCO₃, H₃BO₃, Li₂CO₃, Na₂CO₃, K₂CO₃, Eu₂O₃, Sm₂O₃, Tb₄O₇, CeO₂ and Dy₂O₃ as starting materials. The emission and excitation spectra were measured by a SHIMADZU RF-540 UV spectrophotometer. And the results show that these phosphors can be excited effectively by near-ultraviolet light-emitting diodes (UVLED), and emit red, green and blue light. Consequently, these phosphors are promising phosphors for white light-emitting diodes (LEDs). Under the condition of doping charge compensation Li⁺, Na⁺ and K⁺, the luminescence intensities of these phosphors were increased.     

Intense up-conversion emissions of Yb3+/Dy3+ co-doped Al2O3 nanopowders prepared by non-aqueous sol—gel method

Yb³⁺/Dy³⁺ co-doped Al₂O₃ nanopowders have been prepared by the non-aqueous sol-gel method and their up- conversion photoluminescence spectra are measured under excitation by 980-nm semiconductor laser. The results show that there are comparatively abundant spectra of up-conversion emissions centered at 378, 408, 527 and 543, and 663 nm, corresponding to ⁴G_9/2 → ⁶H_13/2, ⁴G_9/2 → ⁶H_11/2, ⁴I_15/2 → ⁶H_13/2, and ⁴F_9/2 → ⁶H_11/2 transitions of Dy³⁺, respectively. Two-photon and three-photon processes are involved in ultraviolet, violet, green, and red up-conversion emissions. The energy transition between Yb³⁺ and Dy³⁺ is discussed.     

Additivity and non-additivity of dissociation energies in intermolecular interactions. Theoretical studies on (H2)n,n = 2-8, (CO2)n,n = 2-6 and (HF)n,n = 2-8

CCSD(T) and MP2 results using the aug-cc-pV5Z basis set are reported for chain, cyclic and other structures of the clusters (H₂)_n, n?=?2-8, (CO₂)_n, n?=?2-6 and (HF)_n, n?=?2-8. In chain-like structures of (H₂)_n and (CO₂)_n, with the bonding type of the dimer maintained, the dissociation energy D_e of the dimer doubles for the trimer, triples for the tetramer, and so on. Due to these systems being dominated by short-range forces, interactions are essentially restricted to neighbouring monomers. For other types of (H₂)_n and (CO₂)_n structures, the multipliers relative to the dimerisation energy can be much higher. Dissociation energies for the hexamers in S₆ symmetry of both H₂ (379?cm^?1) and CO₂ (4925?cm^?1) are over ten times the respective dimerisation energies. For the chain-like trimer of HF, however, D_e is in excess of double the dimer value. Mainly due to longer-range dipolar forces, the interactions reach beyond the neighbouring monomers. The interaction energy between HF monomers in chains follows an approximate R^?2 (R being the F–F distance) relationship, The calculated dissociation energies of the HF octamer are 15,985?cm^?1 (factor of 10.4) for the chain, and 21,003?cm^?1 (factor of 13.7) for the C_6h cyclic structure.     

Enhanced luminescence of Dy in Y3Al5O12 by Bi co-doping

In the present paper, phosphors with the composition Y_3−x−yAl₅O₁₂:Bi³⁺_x, Dy³⁺_y were synthesized with solid state reactions. The luminescence properties of Bi³⁺ and Dy³⁺ in Y₃Al₅O₁₂(YAG) and the energy transfer from Bi³⁺ to Dy³⁺ were investigated in detail. Bi³⁺ in YAG emits one broad band peaking at 304 nm which can be ascribed to the transition from excited states ³P_{0, 1} to ground state ¹S₀. Dy³⁺ in YAG emits two groups of peaks around 484 and 583 nm, respectively, which can be ascribed to the transitions from excited state ⁴F_9/2 to ground states ⁶H_15/2 and ⁶H_13/2. The co-doping of Bi³⁺ enhances the luminescent intensity of Dy³⁺ by ∼7 times because Bi³⁺ can transfer the absorbed energy to Dy³⁺ efficiently. The mechanism of energy transfer was also discussed.     

Synthesis and characterization of Sr3Al2O6：Eu2＋, Dy3＋ phosphors prepared by sol-gel-combustion processing

A type of red luminescent Sr3Al2O6:Eu2+, Dy3+ phosphor powder is synthesised by sol-gel-combustion processing, with metal nitrates used as the source of metal ions and citric acid as a chelating agent of metal ions. By tracing the formation process of the sol-gel, it is found that it is necessary to reduce the amount of NO3- by dropping ethanol into the solution for forming a stable and homogeneous sol-gel. Thermogravimetric and Differential Scanning Calorimeter Analysis, x-ray diffractionmeter, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the luminescent properties of the as-synthesised Sr3Al2O6:Eu2+, Dy3+. The results reveal that the Sr3Al2O6 crystallises completely when the combustion ash is sintered at 1250 C. The excitation and the emission spectra indicate that the excitation broadband lies mainly in a visible range and the phosphors emit a strong light at 618 nm under the excitation of 472 nm. The afterglow of (Sr0.94Eu0.03Dy0.03)3Al2O6 phosphors sintered at 1250 ℃ lasts for over 1000 s when the excited source is cut off.     

Flame structure studies of rich ethylene-oxygen-argon mixtures doped with CO2, or with NH3, or with H2O

Structures of several premixed ethylene-oxygen-argon rich flat flames burning at 50 mbar have been established by using molecular beam mass spectrometry in order to investigate the effect of CO₂, or NH₃, or H₂O addition on species concentration profiles. The aim of this study is to examine the eventual changes of profiles of detected hydrocarbon intermediates which could be considered as soot precursors (C₂H₂, C₄H₂, C₅H₄, C₅H₆, C₆H₂, C₆H₄, C₆H₆, C₇H₈, C₆H₆O, C₈H₆, C₈H₈, C₉H₈ and C₁₀H₈). The comparative study has been achieved on four flames with an equivalence ratio (f) of 2.50: one without any additive (F2.50), one with 15% of CO₂ replacing the same quantity of argon (F2.50C), one with 3.3% of NH₃ in partial replacement of argon (F2.50N) and one with 13% of H₂O in replacement of the same quantity of argon (F2.50H). The four flat flames have similar final flame temperatures (1800 K).CO₂, or NH₃, or H₂O addition to the fresh gas inlet causes a shift downstream of the flame front and thus flame inhibition. Endothermic processes CO₂ + H = CO + OH and H₂O + H = H₂ + OH are responsible of the reduction of the hydrocarbon intermediates in the CO₂ and H₂O added flames through the supplementary formation of hydroxyl radicals. It has been demonstrated that such processes begin to play at the end of the flame front and becomes more efficient in the burnt gases region.The replacement of some Ar by NH₃ is responsible only for a slight decrease of the maximum mole fraction of C₂H₂, but NH₃ becomes much more efficient for C₄H₂ and C₅ to C₁₀ species. Moreover, the efficiency of NH₃ as a reducing agent of C₅ to C₁₀ intermediates is larger than that of CO₂ and H₂O for equal quantities added.     

Specific features of photo and thermoluminescence of Tb ions in BaO-M2O3 (M=Ga, Al, In)-P2O5 glasses

BaO-P₂O₅ glasses mixed with the three metal oxides viz., Al₂O₃, Ga₂O₃ and In₂O₃ doped with Tb₂O₃ were prepared. The glasses were characterized by X-ray diffraction and differential thermal analysis. Optical absorption and photoluminescence spectra and thermoluminescence (TL) of these glasses have been studied. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated and compared with those of other reported glass systems. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of TL data indicate high non-radiative losses in In₂O₃ mixed glasses.     

Density functional analysis of the magnetic structures of Sr2MGe2O7 (M=Mn,Co)

To examine the difference between the magnetic structures of Sr₂MGe₂O₇ (M=Mn, Co), we evaluated their spin exchange interactions by performing energy-mapping analysis based on density functional theory calculations. The calculated intra- and inter-layer spin exchanges correctly predict the G-type and C-type antiferromagnetic structures of Sr₂MnGe₂O₇ and Sr₂CoGe₂O₇, respectively, and the Curie–Weiss temperatures estimated from these spin exchanges are also in good agreement with the experiment. The ∥c and ⊥c orientations of the spins in the ordered magnetic structures of Sr₂MnGe₂O₇ and Sr₂CoGe₂O₇, respectively, were also examined by considering spin–orbit coupling.     

Theoretical explanation for the DNA cleavage by GO with cation: anti-cooperativity effect among the π⋯π, cation⋯π/σ and H-bonding interactions in cytosine⋯GO⋯Mn+ (Mn+ = Na+, Mg2+, Al3+)

In order to reveal the nature of DNA cleavage by inorganic intercalator GO (graphene oxide) with cation, the cooperativity effects among the π?π, cation?π/σ and H-bonding interactions were evaluated in the cytosine?GO?Mⁿ⁺ (Mⁿ⁺?=?Na⁺, Mg²⁺, Al³⁺) model systems using the M06-2X, MP2 and ω B97X-D methods with the 6-311++G(2d,p) and 6-311++G(3df,3pd) basis sets. The Mⁿ⁺?O (ether) and N–H?O interactions induce the formation of the π?π stacking between cytosine and GO, and the anti-cooperativity effect are dominant in controling of the aggregation process of cytosine, GO and Mⁿ⁺, which was confirmed by the AIM (atoms-in-molecules) and RDG (reduced density gradient) analyses. Furthermore, the solvent effects of H₂O weaken greatly the anti-cooperativity effects. Thus, a deduction on the DNA cleavage by GO?cation with the intercalation mode is put forward: due to the anti-cooperativity effect and solvent effect, the π?π stacking is weakened in the complexes with Na⁺ or broken in those with Mg²⁺ or Al³⁺. Then the GO?Mg²⁺ moiety is squeezed out from the intercalating sites, leading to an invalid cleavage of DNA, while Na⁺ or Al³⁺ is bound tightly to cytosine, with a notable DNA cleavage. This deduction was used to explain reasonably the previous experimental phenomena.     

绿宝石晶体中(CrO6)9－团簇局域极化现象的理论研究

基于配位场理论,建立d³组态离子在三角晶场中的完全能量矩阵,采用完全能量矩阵的对角化计算方法,研究了绿宝石晶体Cr³⁺：Be₃Al₂(SiO₃)₆的光谱和EPR谱,理论值与实验值符合得很好.通过分析绿宝石晶体中(CrO₆)^9-团簇的光谱和EPR谱,研究了配体在络合物中的极化现象.结果表明由于周围配位环境的影响,绿宝石晶体中(CrO< 关键词： 3+：Be₃Al₂(SiO₃)₆体系')" href="#">Cr³⁺：Be₃Al₂(SiO₃)₆体系 光谱 EPR谱 局域结构极化     

Luminescent properties of green- or red-emitting Eu-doped Sr3Al2O6 for LED

Eu²⁺-doped Sr₃Al₂O₆ (Sr_3−xEu_xAl₂O₆) was synthesized by a solid-state reaction under either H₂ and N₂ atmosphere or CO atmosphere. When H₂ was used as the reducing agent, the phosphor exhibited green emission under near UV excitation, while CO was used as the reducing agent, the phosphor mainly showed red emission under blue light excitation. Both emissions belong to the d-f transition of Eu²⁺ ion. The relationship between the emission wavelengths and the occupation of Eu²⁺ at different crystallographic sites was studied. The preferential substitution of Eu²⁺ into different Sr²⁺ cites at different reaction periods and the substitution rates under different atmospheres were discussed. Finally, green-emitting and red-emitting LEDs were fabricated by coating the phosphor onto near UV- or blue-emitting InGaN chips.     

The electron affinity of Al13H cluster: high level ab initio study

Al₁₃H clusters have been considered candidates for cluster assembled materials. Here we have carried out benchmark calculations for the Al₁₃H cluster, both neutral and anionic, with the aim of verifying the nature of stationary points on the potential energy surface, studying dynamics of H atom and determining an adiabatic electron affinity. A range of correlated methods applied include second-order perturbation theory (MP2), spin-component-scaled MP2, coupled electron pair (CEPA) and coupled cluster singles and doubles with perturbative triple corrections (CCSD(T)). These methods are used in combination with the correlation consistent basis sets through aug-cc-pVTZ including extrapolation to the complete basis set (CBS) limit. Performance of several different flavours of density functional theory (DFT) such as generalised gradient approximation (GGA), hybrid GGA, meta-GGA and hybrid-meta-GGA is assessed with respect to the ab initio correlated reference data. The harmonic force constant analysis is systematically performed with the MP2 and DFT methods. The MP2 results show that for neutral Al₁₃H only the hollow structure is a potential energy minimum, with the bridged structure being a transition state for the H shift from the hollow site to the adjacent hollow site. The CCSD(T)/aug-cc-pVTZ (CCSD(T)/CBS) estimate of the energy barrier to this H shift is 2.6 (2.9) kcal/mol, implying that the H atom movement over the Al₁₃H cluster surface is facile. By contrast, the DFT force constant analysis results suggest additional terminal and bridged minima structures. For the anion Al₁₃H^?, exhibiting ‘stiffer’ potential energy surface compared to the neutral, the existence of the hollow and terminal isomers is consistent with the earlier photoelectron spectroscopy assignment. The adiabatic electron affinity of Al₁₃H is determined to be 2.00 and 1.95 eV (the latter including the ΔZPE correction) based on the CCSD(T) energies extrapolated to the CBS limit, whereas the respective CCSD(T)/CBS thermodynamic EA values are 2.79 and 2.80 eV.     

Effect of boric acid on structure,morphology and luminescent properties of divalent europium doped calcium aluminate phosphors

Blue phosphors Ca_1 − xAl₂O₄: xEu²⁺ were prepared by high temperature solid-state method. Their structure, morphology and luminescent properties were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and fluorescence spectroscopy. The effect of different amounts of fluxing agent H₃BO₃ on structure, morphology and luminescent properties of blue phosphors Ca_1 − xAl₂O₄: xEu²⁺ luminous intensity caused by different amount of H₃BO₃ was also investigated. The amount of H₃BO₃ doped Ca_1 − xAl₂O₄: xEu²⁺ in optimal luminous intensity had been determined. The results showed that both the excitation and emission spectra of samples were all broad bands, and that the peak of emission spectra was near 442 nm, which was corresponding to the 4f⁶5d → 4f⁷ transition of Eu²⁺ illuminating blue light. Ca_1 − xAl₂O₄: xEu²⁺ (x = 3.5 mol%) could be gained with good morphology and the best luminous intensity when H₃BO₃ mass ratio was 0.5 wt%.     

Eu2+, Cr3+共掺杂的MAl12O19 (M=Ca, Sr, Ba) 的发光性质及能量传递

三基色荧光粉中, 红色荧光粉性能较差, 为获得性能优良的红色荧光粉, 本文采用高温固相法合成了Eu²⁺, Cr³⁺单掺杂及共掺杂的碱土金属多铝酸盐MAl₁₂O₁₉ (M =Ca, Sr, Ba) 发光体. 实验表明, 在以上三种基质中均存在Eu²⁺→Cr³⁺的能量传递, 利用能量传递可以有效将Eu²⁺的蓝光或绿光转换为红光. 三种碱土金属多铝酸盐基质的晶体结构相似,但Eu²⁺, Cr³⁺发光受晶体场影响,导致在不同的基质中Eu²⁺, Cr³⁺间能量传递效率不同.通过光谱分析及能量传递效率计算发现, 相同掺杂浓度下,CaAl₁₂O₁₉中Eu²⁺→Cr³⁺的能量传递效率最高,SrAl₁₂O₁₉次之, BaAl₁₂O₁₉最低.红光转换率在CaAl₁₂O₁₉中最高.     

Ab Initio Study on Structures and Vibrational Spectra of M+(H2O)Ar2 (M = Cu,Au)

Previous investigations have shown that it is difficult to acquire the infrared (IR) spectra of M⁺(H₂O) (M?=?Cu, Au) using a single IR photon by attaching an Ar atom to M⁺(H₂O). To explore whether the IR spectra can be obtained using the two Ar atoms tagging method, the geometrical structures, IR spectra and interaction energies are investigated in detail by ab initio electronic structure calculations for M⁺(H₂O)Ar₂ (M?=?Cu, Au) complexes. Two conceivable isomeric structures are found, which result from different binding sites for two Ar atoms. CCSD(T) calculations predict that two Ar atoms are most likely to attach to Cu⁺ for the Cu⁺(H₂O)Ar₂ complex, while the Au⁺(H₂O)Ar₂ complex prefers the isomer in which one Ar atom attaches to an H atom of the H₂O molecule and the other one is bound to Au⁺. Moreover, the calculated binding energies of the second Ar atom are smaller than the IR photon energy, and so it is possible to obtain the IR spectra for both Cu and Au species. The changes in the spectra caused by the attachment of Ar atoms to M⁺(H₂O) are discussed.     

A systematic investigation of the geometries,electronic and magnetic properties of AlnAsq (q = −1, 0, +1; n = 1–16) clusters: a DFT calculation

The geometries, electronic and magnetic properties of Al_nAs^q (q = ?1, 0, +1; n = 1–16) clusters have been investigated systematically by using an unbiased CALYPSO structure searching method and density functional theory. The lowest energy structures show that the As atom prefers to occupy the peripheral position of Al_n+1 clusters instead of the endohedral position. For cationic and neutral clusters, the structural transition from bilayer-like structure to cage-like structure is observed at cluster size n = 12, while it occurs at n = 13 for anionic clusters. The calculated detachment energies (DEs), ionisation potentials (IPs) and electronic affinities (EAs) are consistent with the available experimental and theoretical results for small clusters, indicating that the calculated lowest energy structures are reliable. Furthermore, the DE, EA and IP values for cluster size n ≥ 6 are successfully predicted. A stability analysis shows that Al₅As and Al₁₂As⁺ clusters have relatively large HOMO–LUMO energy gaps, corresponding to the magic numbers of 20 and 40 valence electrons, respectively.     

GREAT MAGNETIC ENTROPY CHANGE IN La(Fe, M)13 (M=Si, Al) WITH Co DOPING

Very large magnetic entropy change Δ S_M, which originates from a fully reversible second-order transition at Curie temperature T_C, has been discovered in compounds La(Fe, Si)₁₃, La(Fe, Al)₁₃ and those with Co doping. The maximum change ΔS_M\approx19 J·kg^-1·K^-1, achieved in LaFe_11.4Si_1.6 at 209K upon a 5T magnetic field change, exceeds that of Gd by more than a factor of 2. The T_C of the Co-doped compounds shifts to higher temperatures. ΔS_M still has a considerable large magnitude near room temperature. The phenomena of very large ΔS_M, convenience of adjustment of T_C, and also thesuperiority of low cost, strongly suggest that the compounds La(Fe, M)₁₃ (M=Si, Al) with Co doping are suitable candidates for magnetic refrigerants at high temperatures.     

Lifetimes of rovibrational levels of the long-range I′ 1Πg state of H2 and D2: experiment and theory

The lifetimes of the lowest lying rovibrational levels of the outer well I′ ¹Π_g state of molecular hydrogen were measured for both H₂ and D₂. The measurements were made by direct observation of the time-dependent decay of the fluorescence. The observed lifetimes depend on isotopomer and increase with vibrational excitation. The predominant decay route for these levels is fluorescence. Previously published ab initio lifetimes calculated for these states, which accounted for non-adiabatic interactions [J. Chem. Phys. 92, 7461 (1990)], are in good agreement with experiment for H₂ but are too long by four or five orders of magnitude for D₂. We present new ab initio results at the adiabatic level for the fluorescence lifetimes. The current results are in reasonable agreement with the experimental lifetimes for both H₂ and D₂. We explain the isotopomer and vibrational dependence of the lifetimes and discuss the neglected interactions and decay pathways.     

三明治结构Tan(B3N3H6)n+1 团簇的磁性和量子输运性质

利用密度泛函理论和非平衡格林函数方法, 本文对小尺寸团簇Ta_n(B₃N₃H₆)_n+1 (n ≤ 4)的磁性和量子输运性质进行了系统的研究. 计算结果表明, 此类体系采用三明治结构作为其基态并且具有较高的稳定性. 体系的磁矩随团簇尺寸的增大而线性增大. 当把Ta_n(B₃N₃H₆)_n+1团簇耦合到Au电极上时, 形成的Au-Ta_n(B₃N₃H₆)_n+1-Au体系在有限偏压下展示出了较强的自旋过滤能力, 因而可以被看做是一类新型的低维自旋过滤器.