Ta4Cn^-/0(n=0-4)团簇的电子结构、成键性质及稳定性

本文采用尺寸选择的负离子光电子能谱技术,结合密度泛函理论,对Ta4Cn^-/0(n=0-4)团簇电子结构、成键性质以及稳定性进行了研究.实验测得Ta4Cn-(n=0—4)团簇负离子基态结构的垂直脱附能分别为(1.16±0.08),(1.35±0.08),(1.51±0.08),(1.30±0.08)和(1.86±0.08)eV.中性Ta4Cn(n=0—4)团簇的电子亲和能分别为(1.10±0.08),(1.31±0.08),(1.44±0.08),(1.21±0.08)和(1.80±0.08)eV.研究发现Ta4^-/0团簇为四面体结构,Ta4C1-/0团簇中碳原子覆盖在Ta4四面体的一个面上方,Ta4C2^-/0团簇则是两个碳原子分别覆盖在Ta4四面体中的两个面上方.Ta4C3^-/0团簇是一个缺角立方体结构.Ta4C4^-/0团簇则是近似立方体结构,可以看成是α-TaC面心立方晶体的最小晶胞单元.分子轨道分析结果显示Ta4C3团簇的单电子最高占据轨道主要布居在单个钽原子周围,导致Ta4C3^-团簇的垂直脱附能明显低于其相邻团簇.理论研究显示随着碳原子数目的增加,Ta4Cn^-/0(n=0—4)团簇中的钽-钽金属键逐渐被钽-碳共价键取代,单原子结合能逐渐增加且明显高于Ta4+n^-/0(n=0-4)团簇.中性Ta4C4的单原子结合能高达7.13 eV,这说明钽-碳共价键的形成有利于提高材料的熔点,这与碳化钽作为高温陶瓷材料的特性密切相关.     

AlnCl(n=2-14)团簇结构与电子性质的理论研究

运用卡里普索(CALYPSO)结构预测方法,在杂化密度泛函B3LYP/6-311G+(d)基组水平上,对AlnCl(n=2-14)团簇的几何结构与电子性质进行优化计算,并讨论了团簇的平均结合能、能隙、二阶能量差分、电离能、亲和能以及电子自然布局和极化率。研究结果表明：AlnCl(n=2-14)团簇的基态构型由简单平面几何结构向立体结构演化,形成Cl原子戴帽Aln-1Cl团簇结构;Cl原子的掺杂增大了Aln团簇的平均结合能;二阶能量差分、能隙、电离能、亲和能的变化表明Al7Cl是幻数团簇结构;团簇中的电荷总是由Al原子向Cl原子转移,原子之间的成键作用随着团簇尺寸的增大而增强。     

Al_nCl(n=2-14)团簇结构与电子性质的理论研究

运用卡里普索(CALYPSO)结构预测方法,在杂化密度泛函B3LYP/6-311G+(d)基组水平上,对Al_nCl(n=2-14)团簇的几何结构与电子性质进行优化计算,并讨论了团簇的平均结合能、能隙、二阶能量差分、电离能、亲和能以及电子自然布居和极化率.研究结果表明:Al_nCl(n=2-14)团簇的基态构型由简单平面几何结构向立体结构演化,形成Cl原子戴帽Al_n-1Cl团簇结构;Cl原子的掺杂增大了Al_n团簇的平均结合能;二阶能量差分、能隙、电离能、亲和能的变化表明Al_7Cl是幻数团簇结构;团簇中的电荷总是由Al_原子向Cl原子转移,原子之间的成键作用随着团簇尺寸的增大而增强.     

Electron impact ionization of sodium Rydberg atoms below 2 eV

We have observed electron impact ionization of highly excited sodium Rydberg atoms in ns and nd states, n=35-51, below E=2 eV electron kinetic energy with energy resolution 0.25 eV. Measured absolute cross sections near 0 eV range from sigma(35d) approximately 7 x 10(-10) to sigma(50d) approximately 4 x 10(-9) cm(2). The energy dependence is consistent with that of widely used binary encounter approximation cross sections, and sigma(n) follows a power law in n. The measured cross sections are 14 to 24 times larger than theoretically predicted values. This enhancement may signal the effect of large polarizabilities of high Rydberg states not yet accounted for in ionization theories.     

Cross Sections of Electron Detachment for Si^- and Ge^- in Collision with Ar

Single electron detachment cross section for 10-40keV Si^- and Ge^- in collisions with Ar are measured and compared with other available experimental results. In our experimental energy region, the trend of cross sections is almost constant. The cross sections of Ge larger than Si can be understood by including electron affinity and size of negative ions.     

Structure and magnetism of neutral and anionic palladium clusters

The properties of neutral and anionic Pd(N) clusters were investigated with spin-density-functional calculations. The ground-state structures are three dimensional for N>3 and they are magnetic with a spin triplet for 2 < or = N < or = 7 and a spin nonet for N = 13 neutral clusters. Structural and spin isomers were determined and an anomalous increase of the magnetic moment with temperature is predicted for a Pd7 ensemble. Vertical electron detachment and ionization energies were calculated and the former agrees well with measured values for Pd(-)(N).     

Electron-impact detachment from S<Superscript>-</Superscript>

Absolute cross sections for single and double electron-impact detachment of the S^- ion have been investigated over collision energy ranges of 0-60 eV and 0-30 eV, respectively. The experiment was performed at the ion storage ring, CRYRING. The threshold energies were measured to be 6.6 eV for single detachment and 19.8 eV in the case of double detachment. The single detachment cross section has a maximum of 6.7 x 10^-16 cm² at 30 eV. The double detachment cross section was studied only in the threshold region. No sharp structures were observed in either of the cross sections.Received: 24 April 2003, Published online: 29 July 2003PACS: 34.80.Dp Atomic excitation and ionization by electron impact - 34.80.Kw Electron-ion scattering; excitation and ionization     

Formation of higher-order fullerene dianions in collisions with Na atoms

We have measured electron capture cross sections in collisions between higher order fullerene anions C_n ^- (n=76, 78, 82, 84, 86, 90 and 96) and Na atoms. The ions were produced in an electrospray ion source (ESI) and accelerated to an energy of 50 keV. The measured cross section for dianion formation is three times larger for C₉₆ than that for C₆₀. The latter cross section was earlier found to be 36 ?². The dramatic increase of the cross section with fullerene size is explained by means of the curve crossing model for electron transfer.     

Geometries,stabilities, and electronic properties analysis in In_nNi~((0,±1)) clusters: Molecular modeling and DFT calculations

Density functional theory(DFT) with the B3 LYP method and the SDD basis set is selected to investigate In_nNi,In_nNi~-, and In_nNi~+ (n = 1–14) clusters. For neutral and charged systems, several isomers and different multiplicities are studied with the aim to confirm the most stable structures. The structural evolution of neutral, cationic, and anionic In_nNi clusters, which favors the three-dimensional structures for n = 3–14. The main configurations of the In_nNi isomers are not affected by adding or removing an electron, the order of their stabilities is also nearly not affected. The obtained binding energy exhibits that the Ni-doped In_(13) cluster is the most stable species of all different sized clusters. The calculated fragmentation energy and the second-order energy difference as a function of the cluster size exhibit a pronounced even–odd alternation phenomenon. The electronic properties including energy gap(E_g), adiabatic electron affinity(AEA), vertical electron detachment energy(VDE), adiabatic ionization potential energy(AIP), and vertical ionization potential energy(VIP) are studied. The total magnetic moments show that the different magnetic moments depend on the number of the In atoms for charged In_nNi. Additionally, the natural population analysis of In_nNi~((0,±1)clusters is also discussed.     

Binding energies of near proton-drip line Z = 22-28 isotopes determined from measured isotopic cross section distributions

A new method is proposed to determine the binding energy(B)of near proton-drip line isotopes from isotopic cross section distribution.To determine B of Z=22-28 isotopes(with T_z=-2 and-5/2),the lack of cross sections for proton-rich isotopes in the 345A MeV~(78)Kr+~9Be is overcome by predicting the proton-rich isotopes from a newly discovered scaling phenomenon found in the proton-rich isotopes measured in the 140A MeV~(40,48)Ca(~(58,64)Ni)+~9Be reactions.The cross sections for proton-rich isotopes are verified to exponentially depend on the average binding energy per nucleon,based on which B of the Z=22-28 isotopes with T_z=-2 and-5/2 are determined from cross sections.The determined B of the isotopes are justified from obeying the scaling phenomenon of the difference between the mass of mirror nuclei.The cross sections for the Z=22-28 isotopes with T_z=-1 and-3/2,which in potential can be experimentally studied in mass storage ring,are also predicted.     

中性及其带电Cun(n=2-12)团簇体系的第一性原理计算研究

结合半经验原子间势及遗传算法,采用密度泛函理论,系统计算研究了Cun(n=2-12)及Cun±(n=2-12)的基态与低激发态的几何结构与电子结构.结果表明：对中性团簇在n=3-6时基态为平面结构,而对于带电体系n=3-5时基态为低维结构,其中平面结构都以三角形为基本单元;对含更多原子的立体结构,基态主要以五角双锥为基本结构单元,传统的高对称性结构在小铜团簇基态中不占优势;计算所得Cun(n=2-12)中性体系结合能与实验结果完全一致,而结合带电体系计算所得团簇电离能与亲和势也与实验相符合;团簇电子结构的相关曲线（电离能、亲和势、二阶差分能）均呈现明显的奇偶振荡现象,这与含偶数电子Cu团簇的相对高稳定性密切相关。     

中性及其带电Cun(n=2-12)团簇体系的第一性原理计算研究

结合半经验原子间势及遗传算法，采用密度泛函理论，系统计算研究了Cun(n=2-12)及Cun±(n=2-12)的基态与低激发态的几何结构与电子结构.结果表明：对中性团簇在n=3-6时基态为平面结构，而对于带电体系n=3-5时基态为低维结构，其中平面结构都以三角形为基本单元；对含更多原子的立体结构，基态主要以五角双锥为基本结构单元，传统的高对称性结构在小铜团簇基态中不占优势；计算所得Cun(n=2-12)中性体系结合能与实验结果完全一致，而结合带电体系计算所得团簇电离能与亲和势也与实验相符合；团簇电子结构的相关曲线（电离能、亲和势、二阶差分能）均呈现明显的奇偶振荡现象，这与含偶数电子Cu团簇的相对高稳定性密切相关。     

Experimental determination of nucleation scaling law for small charged particles

We investigated the nucleation process at the molecular level. Controlled sticking of individual atoms onto mass selected clusters over a wide mass range has been carried out for the first time. We measured the absolute unimolecular nucleation cross sections of cationic sodium clusters Na{n}{+} in the range n=25-200 at several collision energies. The widely used hard sphere approximation clearly fails for small sizes: not only should vapor-to-liquid nucleation theories be modified, but also, through the microreversibility principle, cluster decay rate statistical models.     

Effects of electron screening on low-energy fusion cross sections

The effects of electron screening on the low-energy cross sections of nuclear fusion reactions of astrophysical interest have been studied within the Born-Oppenheimer approximation using a simplified model. These studies indicate that a significant enhancement of the cross sections can occur already at beam energies, which are about a factor 100 higher than the electron binding energies. Cross sections near such energies can now be measured, in some cases, and several examples are discussed. For an understanding of the low-energy data as well as for a reliable extrapolation of the cross sections (for bare nuclei) to lower energies, the effects of electron screening must be well understood.     

Single electron detachment of carbon group and oxygen group elements incident on helium

The absolute single electron detachment (SED) cross sections of carbon group elements C⁻, Si⁻, Ge⁻ in the energy range of 0.05–0.29 a.u. (5 keV–30 keV) and oxygen group elements O⁻ and S⁻ 0.08–0.27 a.u. (5 keV–30 keV), incident on helium are measured with growth rate method. In our energy region, the SED cross sections of C⁻, Si⁻, S⁻ and Ge⁻ increase with the projectiles velocity, at the same time, O⁻ cross sections reach a conspicuous maximum at 0.18 a.u. Some abnormal behavior occurs in measurement of SED cross sections for the oxygen group collision with helium. Our results have been compared with a previous work.     

Irn(n=2-25)团簇基态结构的遗传算法研究

用遗传算法结合Gupta紧束缚模型势研究了Irn(n=2-25)团簇的基态结构.分析了Irn(n=2-25)团簇的基态结构随团簇尺寸的变化规律.计算结果表明,Irn(n=2-25)团簇的每个原子的平均束缚能和平均第一近邻随团簇尺寸的增加而增大,以总束缚能的二阶差分为判据,Irn(n=2-25)团簇的幻数是4、7、9、13、15、19、23.     

CsSi_n~u(n=2-12;u=±1)团簇结构与电子性质的密度泛函研究

运用卡利普索结构预测方法并结合密度泛函理论中的杂化密度泛函B3LYP方法对CsSi_n~u(n=2-12;u=±1)进行了系统的研究.结果发现:除了CsSi_7~(+1)与CsSi_(2,4,6,10)~(-1)之外,大多数CsSi_n~(±1)团簇的基态结构与对应中性CsSi_n团簇的结构不相同;稳定性分析显示得失电子明显提高了体系的稳定性,CsSi_(4,7,9)~(+1)与CsSi_(2,5)~(-1)分别在对应团簇中具有相对较高的稳定性;Cs原子总是占有正电荷.最后讨论了团簇的电离势、电子亲和能与结构之间的关系.     

55Mn(n,n'γ) cross-section studies for En = 1.0–3.6 MeV

Absolute ⁵⁵Mn(n, n′γ) γ-ray production cross sections have been measured for 19 transitions from levels up to and including the 2429 keV state in ⁵⁵Mn over the energy range E_n = 1.0–3.6 MeV. Angular distributions were also measured for 6 of the transitions. Branching ratios were extracted and total inelastic neutron cross sections were inferred for these ⁵⁵Mn excited states. The measured and inferred cross sections are compared with calculated cross sections using the statistical compound nucleus theory.     

Experiment and theory for the 2H(e,p)e′n reaction

Differential cross sections and angular distributions of protons from the ²H(e, p)e′n reaction have been measured at four incident electron energies. The proton angular distributions were measured with the neutron-proton relative energy approximately constant, and an 85° differential cross section was measured as a function of the incident electron energy. The electrodisintegration cross section was calculated using the Hulthén wave function for the ground state with a plane wave for the final state. Reasonable agreement between experiment and theory is found.     

Appearance of metallic features in small tungsten clusters

The structures and properties of W_n (n=2--14) clusters were studied by using the density functional theory (DFT) at LSDA level. The most stable structures of W_n (n=2--14) clusters with global minimum were determined. The average binding energy (E_b), the first and second difference of total energy (\itδ E, \itδ₂E), the vertical detachment energy (VDE), and the HOMO-LUMO gap versus the size were also discussed. The abrupt decrease of VDE and HOMO-LUMO gap at size n=8 and 10 implied that tungsten clusters of W₈ and W₁₀ appeared to have metallic features. These changes were also accompanied by the delocalization of electron charge density and the strong hybridization between 5d and 6s orbits in W₈ and W_10 clusters. Our results are in good agreement with the available experimental data.