Formation of substitutionalmetallofullerenes by laser ablation of externally doped fullerenes C60Mx (M=Sm, Pt,Ni and Rh)

Photofragmentation study of metal fullerides C60Mx (M=Sm, Pt, Ni and Rh) by excimer laser ablation-TOF mass spectrometry shows that metallofullerenes C2nM and C2n+1M formed in both the positive and negative ionic medes.The isotopic distributions of the metallofullerenes C2nM and C2n+1M are consistent with the calculated spectra based on the natural abundance of isotopes of C and M, confirming the formation of metallofullerenes. The metal atom is supposed to be incorporated into the network of the fullerene cage to replace one carbon atom of the cage forming substitutional metallofullerene. Odd-numbered high carbon cluisters are observed in our laser ablation study of all the metal fullerides in the negative ion channel. Evolution of mass spectrum with irradiation laser shots shows that the formation of the substitutionally doped fullerenes is closely related to the production of metal carbide (MC). The structures, as well as formation mechanism, of metallofullerenes C2n+1Mand C2nM with even and odd numbers of total atoms respectively are discussed based on the structural optimization of the odd-numbered high carbon clusters.     

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^±.     

Experimental and theoretical studies of the reaction between cationic vanadium oxide clusters and acetylene

The time of flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor was adopted to study the reactivity of cationic vanadium oxide clusters （VinOS,） toward acetylene （C2H2） molecules under gas phase （P, - 1.14 kPa）, under near room temperature （T, - 350 K） conditions. Association products, VmOnC2H2^＋ （m,n = 2,4; 2,6; 3,7-8; 4,9-11; 5,12-13; 6,13-16, and 7,17）, are observed. The oxidation of C2H2 by （V2Os）n^＋ （n = 1 -3） is experimentally identified. The reactivity of （V2O5）n^＋ decreases as n increases. Density functional theory （DFT） calculations were carried out to interpret the reaction mechanisms. The DFT results indicate that a terminal oxygen atom from V2O5^＋ can transfer overall barrierlessly to C2H2 at room temperature, which is in agreement with the experimental observation. Other experimental results such as the observation of V206C2H2^＋ and nonobservation of V2O7,8C2H2^＋ in the experiments are also well interpreted based on the DFT calculations. The reactivity of vanadium oxide clusters toward acetylene and other hydrocarbons may be considered in identifying molecular level mechanisms for related heterogeneous catalysis.     

Theoretical study on photophysical property of C60M（CO）5 （M=Cr,Mo and W）

Configurations of three η2 models of transition-metal [60]fullerene derivatives C60M（CO）5（M=Cr, Mo and W） have been optimized at B3LYP/LanL2DZ level. On the basis of the optimized geometrical structures, their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation （THG）, electric-field-induced second-harmonic generation （EFISHG） and degenerate four-wave mixing （DFWM） are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS （sum-over-state） method. The obtained results show that their electronic spectra have a red shift compared with that of [60]fullerene and different transition-metal functional groups added to C60 cage may result in different spectrum properties. For the three studied species, （η^2-C60）Mo（CO）5 has the largest third-order nonlinear optical polarizability.     

Reaction between sulfur dioxide and iron oxide cationic clusters

The reactivity of sulfur dioxide （SO2） molecules toward iron oxide cationic clusters （FemOn^＋） is studied by a homemade time-of-flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor. The association products FemOnSO2^＋ can be observed for most of the clusters. The interesting result is that the cooperation effect of SO2 and water is in favor of the adsorption of gas phase water on specific scale iron oxide clusters （Fe2O2^＋ and Fe3O3^＋ ）. The reactivity information obtained may be useful to investigate atmospheric heterogeneous chemistry of related systems.     

Nbn(n=2-15)小团簇的第一性原理研究

【目的】研究纳米尺寸Nbn小团簇的结构演变过程,为进一步讨论Nbn小团簇的催化氧化性质提供参考。【方法】采用基于密度泛函理论(包括PW91和BLYP函数)的第一性原理计算方法对Nbn(n=2-15)小团簇的几何结构进行优化计算。【结果】随着原子数n的增加,Nbn(n=2-15)小团簇的结构及其特性具有明显的变化,平均每原子结合能(Binding Energy)随着原子数的增加呈递减趋势。【结论】Nbn(n=2-15)小团簇随尺寸变化具有明显的奇偶震荡性,n为偶数时比n为奇数时的结构稳定,其中Nb4、Nb6、Nb8、Nb10、Nb12小团簇结构较为稳定。     

Comparison of the carbon isotope composition of total organic carbon and long-chain <Emphasis Type="Italic">n</Emphasis>-alkanes from surface soils in eastern China and their significance

Surface soil samples collected over a high spatial resolution in eastern China were analyzed for carbon isotope composition （δ^13C） of total organic carbon （TOC） and higher plant-derived long-chain n-alkanes, with the latter reported as weighted mean values. The two sets of δ^13C values are significantly correlated and show similar trends in spatial variation. The spatial distribution of δ^13C shows less negative values in the mid-latitudes between 31°N and 40°N and more negative ones at higher and lower latitudes. This is consistent with previously reported carbon isotope data from surface soil phytoliths in the same region and suggests that the mid-latitude area provides relatively favorable growing condi- tions for C4 plants. Furthermore, δ^13C values of both TOC and long-chain n-alkanes from 12 surface soil samples collected from a small grassland in north China displayed similar carbon isotope values and the difference between paired δ^13C of a soil samples remains relatively constant. Our data demonstrate that in eastern China, soil δ^13C composition of both TOC and long-chain n-alkanes is effective indicators of C3/C4 ratios of the prevailing vegetation. This work suggests that -22‰ and -32‰ are good es- timated end members for the weighted mean δ^13C values of long-chain n-alkanes （C27, C29 and C31 n-alkanes） from soils under dominant C4 or C3 vegetation, allowing us to reconstruct paleovegetation trends.     

High molecular weight (C35 +) n-alkanes of Neogene heavily biodegraded oil in the Qianmiqiao region, North China

With wax content of 1.62%, heavy oil has been produced from the sandstone reservoirs of Neogene Guantao Formation (Ng1^Ⅲ). In the GC and GC-MS RIC profiles of its aliphatic fraction, n-alkanes are totally lost, which shows the result of heavy biodegradedation. However, the remaining trace C₁₃－C₃₆ n-alkanes can be still seen from its m/z 85 mass chromatogram. In addition, a complete series of C₃₅－C₇₃ high molecular weight (HMW) n-alkanes was detected by high-temperature gas chromatography (HTGC). The HMW n-alkane series shows a normal distribution pattern, a major peak at nC₄₃, obvious odd-carbon-number predominance, CP_I37—55 and OEP_45—49 values up to 1.17 and 1.16—1.20 respectively. The present study not only has conformed the strong resistibility of HMW n-alkanes to biodegradation in crude oils as concluded by previous researchers, but also has provided some significant information on source input and maturity for the heavily biodegraded oil in the Qianmiqiao region.     

Carbothermal reduction process of the Fe-Cr-O system

Understanding the reduction behaviors and characteristics of the end products of Fe-Cr-O systems is very important not only for maximizing the recovery of metals from stainless steel dust but also for the subsequent reuse in metallurgical process. The present work first predicted the possible products thermodynamically when FeCr₂O₄ was reduced by C. The reduction behaviors by graphite of three kinds of Fe-Cr-O systems, i.e., FeCr₂O₄, Fe₂O₃+Cr₂O₃, and Fe+Cr₂O₃, were then investigated in 1350–1550℃. Further, the microstructures of final products and element distribution conditions were examined. The results suggest that, thermodynamically, the mass of products for the carbothermal reduction of FeCr₂O₄ is a strong function of temperature, and the initial carbon content is used. More Fe-Cr-C solution and less residual carbon content are obtained at higher temperatures and lower n_C:n_O ratios (the initial molar ratio of C to O in the sample). Experimental data show that the sample amount tends to affect the reduction rate, and the residual carbon content strongly depends on n_C:n_O. With regard to the phases present in products during the reaction process, metal carbides tend to form in the initial stage, whereas Fe-Cr-C solution forms when the degree of reduction is sufficiently high.     

激光蒸发产生的GaxAsy—,GaxPy—与InxPy—及其质谱

在自制的激光等离子体源飞行时间质谱计上,以脉冲激光束轰击砷化镓、磷化镓、磷化铟等由Ⅲ A族和Ⅴ A族元素组成的半导体材料,可以产生Ga_xAs_y~-、Ga_xP_y~-与In_xP_y~-等二元原子簇负离子,质谱分析发现,在这些负离子中,所有含奇数个原子的簇离子的信号强度相对较高,说明这些原子簇均具有特殊的电子构型。     

Structures and stability of (HAlNH)n (n=1－15)

The geometries, electronic states, vibrational spectra and thermodynamic properties for (HAlNH)_n clusters with n=1－15 have been investigated using the ab initio DFT/B3LYP method with basis sets 6-31G* and their ground state structures obtained. Comparison of the (HAlNH)_nwith (AlN)_n clusters shows that the skeletons of (HAlNH)_nconsist of four-membered and six-membered rings made of Al-N bonds, and either Al or N atom forms four bonds in which three ones are Al-N bonds and the rest is Al-H or N-H bond. The number of Al-N bonds of (HAlNH)_n is equal to that of (AlN)_n. The magic number regularity of (HAlNH)_n is n =2, 4, 6, 8, etc., all of which are even numbers.     

不同金属对硼球烯的修饰作用

系统研究了3类金属,包括碱金属(M=Li、Na、K)、碱土金属(M=Be、Mg、Ca)及部分过渡金属(M=Ni、Pd、Pt、Cu、Ag、Au)修饰的B40的结构与稳定性,发现除Na和Ca是内嵌结构稳定以外,其余金属原子都倾向于形成外挂结构.随着金属原子数目的增多,Li,Na,K,Ag的平均结合能变化不大;而Be、Mg、Ca、Ni、Pd、Cu则与B40腰上的4个七元环作用能量上更有利,故当原子数目大于4时,平均结合能有所升高.Pt的原子数目升高到6时,B40笼子的主体已经严重变形.此外,随着金属原子数目增多,Ag原子有可能会团聚成金属团簇,Au不仅会形成小的Au团簇,还会改变B40的主体结构,从而形成更复杂的相结构.Bader电荷分析表明,碱金属和碱土金属与B40笼子的离子作用更强,而过渡金属原子则主要以共价作用或配位作用与B40相结合.该研究结果表明Ni有可能是稳定B40笼子的较好选择,其次是Pd.Ni、Pd的掺杂有可能帮助实验实现这一特殊硼球烯结构的制备.     

BLim1/2+(m=6、7)团簇的结构及储氢性能的研究

为开发新型储氢材料提供更为丰富的理论基础,采用B3LYP泛函在6-311++G(d,p)基组水平上对BLi₆⁺超碱团簇和BLi₇²⁺超碱土团簇的稳定性结构、电荷分布等方面进行理论研究,进而研究团簇的储氢性能。结果表明：两个离子团簇均比它们所对应的中性团簇均具有较高的动力学稳定性。两个离子团簇中的每个Li原子同时有效吸附2个氢分子,BLi₆⁺团簇中氢分子在团簇表面平均吸附能为0.969~2.162kCal/mol,储氢质量分数达31.56wt%。而BLi₇⁺团簇中氢分子在团簇表面平均吸附能为1.764~3.714kCal/mol,储氢质量分数达32.21wt%。它们的储氢性能表明BLi₆⁺团簇和BLi₇²⁺团簇均有望成为良好的储氢媒介。     

Y_CΩ_(2n)are easy terms

For any natural number n≥1, Y CΩ 2n is an easy term; that is, for any λ term M, λβ+Y\-CΩ 2n =M is consistent, where Y C is Curry fixed point combinator, Ω 2n ≡ω 2n ω 2n and ω 2n ≡λx.xx...x (there are 2n occurrences of x after λx ). This result is a partial solution to Jacopini's conjecture: Y CΩ n is an easy term for any natural number n≥2.     

NLi4+超碱团簇的结构及储氢性能的理论研究

采用密度泛函理论（B3LYP）方法,在6-311++G（d,p）基组水平上对NLi₄超碱团簇和NLi₄⁺超碱离子团簇的几何结构和稳定性等物理化学性质进行理论计算,进而研究NLi₄团簇和NLi₄⁺团簇的储氢性能。结果表明：NLi₄团簇和NLi₄⁺团簇结构稳定性均比较高,但是通过理论计算表明NLi₄团簇不能有效吸附氢分子,而NLi₄⁺团簇在吸附氢分子过程中不仅结构稳定,而且NLi₄⁺团簇中的每一个锂原子均可有效吸附3个氢分子,氢分子平均吸附能为1.517~2.931 kCal/mol,储氢质量分数达36.67 wt%,合适的吸附能和较高储氢容量表明NLi₄⁺团簇可有望成为良好的储氢材料。     

The occurrence and significance of C25HBI in Cenozoic saline lacustrine source rocks from the Western Qaidam Basin,NW China

The saline lacustrine deposit of the Oligocene Lower Ganchaigou Formation is the main source rock for the Western Qaidam Basin,NW China.In this study,abundant highly branched isoprenoids with 25 carbon atoms (C25HBI) were detected in the upper section of the Lower Ganchaigou Formation.C25HBI is a biomarker for diatoms,and can provide information regarding biogeochemical processes during production and preservation of sedimentary organic matter.The carbon isotopic values of C25HBI in these source rocks were in the range of-18‰ to-20‰.The relative enrichment in 13C of C25HBI suggests that these isoprenoids were derived from diatom blooms.In this case,the diatoms used HCO3-as an additional carbon source to dissolved CO2 in water column due to their high biological productivity.Conversely,the diatom blooms indicated an abundant nutrient supply to the environment and high primary productivity.Thus,the occurrence of 13C-enriched C25HBI could be an ideal marker for good source rocks.The decreased concentration of CO2(aq) in the water column induced by diatom blooms can result in an enrichment in 13C of organic matter synthesized by primary producers.This may be a possible reason for the occurrence of 13C-enriched organic matter in the Cenozoic source rocks of the Western Qaidam Basin.Previous studies have shown that the high carbon number n-alkanes sourced from diatoms have no carbon preference.Hence,the sources of n-alkanes in regional source rocks are complex,and should be considered when discussing the sources of organic matter in future studies.     

碱土金属卤化物理化性质QSPR的研究

根据无机物成键原子的结构特征,提出用新的方法：δi^S=（mizi＋ziEi）/2ninj来计算无机分子中原子特征值δi^S,构建新的拓扑指数^mS.用^0S、^1S作为分子结构特征描述符,通过Statistica5.0软件进行多元线性回归,按照标准偏差取最小,相关系数取最大的原则,建立碱土金属卤化物的物理化学性质Pi与分子结构描述符（^0S、^1S）之间的定量相关方程,并对相关关系进行显著性检验.结果表明,新的拓扑指数对分子结构选择区分性高,具有比较高的相关性和精度,并且计算简便,物理意义明确,建立的各种方程得出的各种物理化学性质预测值与实验值之间能很好地吻合,比其他文献方法更具有广泛性.     

Synthesis, characterization and catalytic hydrosilylation activity of [60] fullerene n-propylamine platinum, rhodium complex

Fullerenen-propylamine platinum, rhodium complex have been prepared from C₆₀ via amination withn-propylamine, then reacting respectively with potassium chloroplatinite or rhodium chloride. The two noble metal complexes can effectively catalyze hydrosiiylation of olefins with triethoxysilane. The Pt complex exhibits high regioselectivty for styrene, nearly 100% branched product is obtained. Supported by the National Natural Science Foundation of China (Grant 29573115) Fang Pengfei: born in 1971, Ph. D     

Synthesis of fullerene hydrazine derivatives

C₆₀/C₇₀ mixture reacts with hydrazine hydrate catalysed by tetrabutylammonium bromide (TBAB) in the presence of air to afford fullerene hydrazine derivatives C₆₀(OH) _n (NHNH₂) _n and C₇₀(OH) _n (NHNH₂) _n , which are characterized by means of MS and FTIR. A possible reaction mechanism is discussed. Shen Shengwen: born in 1971, Master     

碱金属锂原子修饰硅原子链团簇的结构和储氢性能

采用密度泛函理论(DFT)方法研究Li2Sim(m=2,4,6)链状团簇结构及其储氢性能。研究结果表明,氢分子在碱金属Li原子修饰的三种硅链结构中均发生吸附,并且每个Li原子都可以吸附多个氢分子,其中两个Li原子修饰Si2链的结构能够吸附氢分子的储氢质量分数达18.6 wt%,氢分子的平均吸附能为1.850 kcal/moL。结果表明,碱金属Li原子修饰的硅链在室温条件下可作为氢气的存储媒介。