ConC3-/0和ConC4-/0(n=1~4)团簇的结构和电子特性:尺寸选择的负离子光电子能谱和密度泛函理论研究

We investigated the structural evolution and electronic properties of Co_nC₃^-/0 and Co_nC₄^-/0 (n=1-4) clusters by using mass-selected photoelectron spectroscopy and density functional theory calculations. The adiabatic and vertical detachment energies of Co_1-4C₃^- and Co_1-4C₄^- were obtained from their photoelectron spectra. By comparing the theoretical results with the experimental data, the global minimum structures were determined. The results indicate that the carbon atoms of Co_nC₃^-/0 and Co_nC₄^-/0 (n=1-4) are separated from each other gradually with increasing number of cobalt atoms but a C₂ unit still remains at n=4. It is interesting that the Co₂C₃^- and Co₂C₄^- anions have planar structures whereas the neutral Co₂C₃ and Co₂C₄ have linear structures with the Co atoms at two ends. The Co₃C₃^- anion has a planar structure with a Co₂C₂ four-membered ring and a Co₃C four-membered ring sharing a Co-Co bond, while the neutral Co₃C₃ is a three-dimensional structure with a C₂ unit and a C atom connecting to two faces of the Co₃ triangle.     

ConCm±(n=1-5; m=1,2)团簇的密度泛函理论研究

本文采用基于自旋极化的密度泛函理论系统研究了Co_nC_m^± (n=1-5; m=1,2)团簇的几何结构和电子结构特性. 将Co_nC^± (n=2-5)团簇中的一个Co替换为C原子, 个体的基态几何结构发生明显变化; 在Co_nC₂^± (n=1-5)团簇的生长序列中, 发现从n=3开始团簇中的两个C原子有彼此分离分布的趋势, 我们分析, 这是Co金属能够维持单壁碳纳米管(SCNTs)保持开口生长, 成为非常有效的一种催化剂的重要原因. 同时, 将Co_nC^± (n=2-5)团簇中添加一个Co原子后系统的总磁矩出现大幅下降的趋势, 但仍保持奇偶交替的规律. 通过比较中性及带电的Co_nC以及Co_nC₂ (n=1-5)团簇的碎裂能, 本工作发现: 由实验获取的SCNTs应均为带正电的体系, 这一结论与已有的实验模型拟合得很好.     

Symmetry-adapted linear combinations for the eigenvalues and eigenvectors of reciprocal graphs

ABSTRACT

Three classes of reciprocal graphs, viz. monocycle (G^C_n), linear chain (G^L_n) and star (G^K_n) with reciprocal pairs of eigenvalues (λ, 1/λ), are well known. Reciprocal graphs of monocycle (G^C_n) and linear chain (G^L_n) are obtained by putting a pendant vertex to each vertex of simple monocycle (C_n) and simple linear chain (L_n), respectively. A star graph of such kind is obtained by attaching a pendant vertex to the central vertex and to each of the (n ? 1) peripheral vertices of the star graph (K_{1, (n?1)}). An n-fold rotational axis of symmetry for G^C_n and (n ? 1)-fold rotational axis of symmetry for G^K_n have been exploited for obtaining their respective condensed graphs. The condensed graph for G^L_n has been generated from that of G^C_n incorporating proper boundary conditions. Condensed graphs are lower dimensional graphs and are capable of keeping all eigeninformation in condensed form. Thus the eigensolutions (i.e. the eigenvalues and the eigenvectors) in analytical forms for such graphs are obtained by solving 2 × 2 or 4 × 4 determinants that in turn result in the charge densities and bond orders of the corresponding molecules in analytical forms. Some mathematical properties of the eigenvalues of such graphs have also been explored.     

The oxidation of fullerene [C70] with various oxidants by ultrasonication

The reaction of C₇₀ by ultrasonication with various oxidants such as 3-chloroperoxy benzoic acid (Fluka 99%), 4-methyl morpholine N-oxide (Aldrich 97%), chromium (VI) oxide (Aldrich 99.9%), and oxone^® monopersulfate compound, at room temperature causes the oxidation of fullerene [C₇₀(O)_n] (n=1–2 or n=1). The FAB-MS, UV–visible, FT-IR spectra, and HPLC analysis confirmed that products of fullerene oxidation are [C₇₀(O)_n] (n=1–2 or n=1).     

纳秒激光诱导C60分子碎裂中轻碎片离子C+n(n＜30)的产生机理研究

采用飞行时间质谱计测量了纳秒激光诱导C₆₀分子碎裂中轻碎片离子C⁺_n(n≤11)的初始平均动能,结果显示轻碎片离子具有相同的初始平均动能(约为0.34eV),并且该动能在一定范围内不随激光通量的变化而明显改变.结合前人的实验结果,对纳秒激光诱导C₆₀分子碎裂中轻碎片离子C⁺_n(n＜30)的主要产生模式作了新的阐述,即C< 关键词： 飞行时间质谱计 轻碎片离子 笼形结构塌陷 初始动能     

Electronic structures of imidazolium-based ionic liquids

Electronic structures of ionic liquids formed by 1-buthyl-3-alkylimidazolium ion [C_nmim]⁺ (n = 4 and 8) with various inorganic and organic anions have been investigated by ultraviolet photoemission, X-ray photoemission, inverse photoemission and soft X-ray emission spectroscopies (SXES). The comparison of the calculated density of states with the observed spectra revealed that the molecular orbital energies of these ionic liquids are significantly affected by the electrostatic Madelung potential among the ions. The SXES results clearly show that the both highest occupied and lowest unoccupied states of [C₄mim]⁺PF₆⁻ are derived from the cation as a result of strong Madelung potential. On the other hand, the SXES results show the valence electronic structures of ionic liquids with larger anion molecules, [C_nmim]⁺Tf₂N⁻ and [C_nmim]⁺OTf⁻ are contributed from the both cation and anion.     

Electronic structure and infrared spectrum of a WnC0＇± （n= 1-6） cluster

W_nC^0,± (n=1-6) clusters are investigated by using the density functional theory (DFT) at the B3LYP/LANL2DZ level. We find that the neutral, anionic and cationic ground state structures are similar within the same size, and constituted by substituting a C atom for one W atom in the structures of W_n+1 clusters. The natural bond orbital (NBO) charge analyses indicate that the direction of electron transfer is from the W atom to the 2p orbital of the C atom. In addition, the calculated infrared spectra of the W_nC^0,± (n=2-6) clusters manifest that the vibrational frequencies of neutral, anionic and cationic clusters are similar in a range of 80 cm^-1-864 cm^-1. The high frequency, strong peak modes are found to be an almost stretched deformation of the carbide atom. Finally, the polarizabilities of W_nC^0,± (n=1-6) clusters are also discussed.     

关于Al_nC和Al_nC~+(n=1—8)团簇结构和稳定性的研究

通过采用7种密度泛函理论DFT方法对AlnC进行计算,所得结果与实验数据比较,选择了B3lyp方法和6-311G(d)基组对AlnC及AlnC+(n=1—8)团簇进行结构优化和频率分析,得到了AlnC及AlnC+基态以及亚稳态结构.当n从小到大变化时,这些团簇的结构从平面向立体过渡,平面构型以三角形为主,立体构型主要是三棱柱笼状结构;在这些团簇中的高对称性结构中,中性团簇和阳离子只能有其一是稳定构型;在所研究的团簇中,Al2C和Al5C团簇较为稳定.     

Microwave and far-infra-red dielectric absorption inn-alkanes

Summary The power absorption coefficient (α) forn-hexane (C₆),n-heptane (C₇),n-dodecane (C₁₂) andn-tetradecane (C₁₄), benzene and cyclohexane has been studied at 20 °C, in the wave number range 20 to 300 cm⁻¹ within an accuracy of 2%. The power absorption measurements onn-alkanes (C₅−C₁₄ except for C₈, C₁₁ and C₁₃) are discussed in conjunction with the dielectric loss in the frequency range (9⋎140) GHz. The results indicate that, unlike other nonpolar liquids,n-alkanes show a broad dielectric dispersion in the microwave frequency range followed by a second dispersion in the far infra-red. The results are interpreted in terms of a dipole moment of 0.09 D in alkanes. A possible explanation for the origin of the dipole moment is discussed. A reference is also made to measurements of the dielectric loss and the Stark effect on the lower-series alkanes in the gas phase.

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Riassunto Si è studiato il coefficiente di assorbimento di potenza (α) pern-esano (C₆),n-eptano (C₇),n-dodecano (C₁₂) en-tetradecano (C₁₄), nel benzene e nel cicloensano a 20 °C nell’intervallo di numeri d’onda da 20 a 300 cm⁻¹ con un’accuratezza del 2%. Le misurazioni dell’assorbimento di potenza neglin-alcani (C₅−C₁₄, eccetto che per C₈, C₁₁ e C₁₃) sono discusse insieme alla perdita dielettrica nell’intervallo di frequenza (9⋎140) GHz. I risultati indicano che, diversamente da altri liquidi non polari, glin-alcani mostrano un’ampia dispersione dielettrica nell’intervallo di frequenza delle microonde, seguíta da una seconda dispersione nel lontano infrarosso. I risultati sono interpretati in termini di un momento dipolare di 0.09 D negli alcani. Si discute una possibile spiegazione dell’origine del momento dipolare. Si fa anche un accenno alle misurazioni della perdita dielettrica e dell’effetto di Stark sugli alcani della serie inferiore in fase gassosa.

     

Zeeman spectroscopy of the 4 Eu → 2 B 1g phosphorescence of copper porphin in an n-alkane single crystal

The phosphorescence spectrum of the metastable ⁴ E_u state of copper porphin in single crystals of n-octane (C₈) and n-decane (C₁₀) has been studied between 2·3 and 35 K, with and without a magnetic field B. The crystal field splitting between the orbital components observed at 35 K is δ = 30·3 ± 0·3 (C₈), 13·8 ± 0·2 cm^-1 (C₁₀). From the Zeeman shifts we derive the effective orbital angular momentum Λ′ = 0·8 ± 0·2 (C₁₀), the spin-orbit coupling parameter |Z′| = 1·5 ± 1·0 cm^-1 (C₁₀), the spin-spin dipolar interaction parameters D = -0·1 ± 0·2 cm^-1 (C₈, C₁₀) and |E| = 0·31 ± 0·03 cm^-1 (C₈, C₁₀), and the g-factors g _∥ = 2·14 ± 0·04 (C₈, C₁₀) and g _⊥ = 2·00 ± 0·03 (C₈, C₁₀).     

Temperature dependence of the dual phosphorescence from xanthone in n-hexane matrices

The phosphoresence spectrum and lifetime of xanthone embedded in an n-hexane matrix has been investigated as a function of temperature (1·6-100 K). Vibrational analyses of the spectra reveal that emission occurs from three sites, two of which are dominant. Emission from one site (B) occurs from the ³ nπ* state of a planar xanthone molecule and is characterized by strong totally symmetric carbonyl stretching vibrations and a short lifetime (2·4 ms). Emission from the other site (C) is shown to arise from the ³ππ* state of an out-of-plane distorted xanthone molecule. It displays a vibrational structure rich in modes of a ₁, b ₁, and b ₂ (C _2v notation) symmetry and a long lifetime (115 ms). Both direct spin orbit coupling via configurational mixing of the nπ* and ππ* states due to the non-planarity of the molecule in its ³ππ* state and spin-orbit vibronic interaction involving ³ A ₁(ππ*)-¹ A ₂(nπ*) spin-orbit and ¹ A ₂(nπ*)-¹ B ₂(ππ*) vibronic interaction via out-of-plane b ₁ vibrations are shown to be responsible for the C site emission intensity. Vibronic mixing between the ³ππ* and ³ nπ* states is not important. With increasing temperature, the phosphorescence intensity from the B site (³ nπ*) emitters increases at first, reaches a maximum at ～20 K and then decreases. The C site (³ππ*) intensity simply decreases with rising temperature. At a given temperature, the phosphorescence lifetimes are identical and exponential for all emission bands regardless of site origin. These observations indicate an equilibrium between emitters in the two sites throughout the lattice. A phonon-assisted energy transfer mechanism is proposed to account for these observations.     

One-dimensional configuration sums in vertex models and affine Lie algebra characters

We study the local state probabilities of the vertex models in the face formulation associated with the simple Lie algebras X _n =A _n, B _n, C _n, D _n. The corner transfer matrix method expresses them in terms of one-dimensional configuration sums. We show that the latter are the string functions of X _n ⁽¹⁾ modules. We also present similar results for the restricted face models of types B _n ⁽¹⁾, C _n ⁽¹⁾, D _n ⁽¹⁾.     

Reactivity of mixed organozinc and mixed organocopper reagents. Part 4: a kinetic study of group transfer selectivity in C?C coupling of mixed diorganocuprates

The competitive rate data and Taft relationships for the coupling of bromomagnesium n‐butyl (substituted phenyl) cuprates with alkyl bromides show that selective n‐butyl transfer can be explained by an oxidative addition mechanism. Taft reaction constants also show that the residual group FG‐C₆H₄ in the mixed cuprate n‐Bu(FG‐C₆H₄)CuMgBr changes the ability of the copper nucleophile to react with the electrophile RBr. These results provide support for the commonly accepted hypothesis regarding the dependence of the R¹ group transfer ability on the strength of R²? Cu bond in reactions of R¹R²CuMgBr reagents. Copyright © 2009 John Wiley & Sons, Ltd.     

Dissipative tunneling in nanosystems

A quantum dynamical problem has been analytically solved for a two-level system where localized states L ₀ and R ₀ are strongly coupled with reservoirs of local oscillations {L _n } and {R _n }. It is additionally assumed that the spectra of reservoirs are equidistant and the coupling constants are the same. It has been shown that the evolution of states L ₀ and R ₀ in recurrence cycles depends on three independent factors, which characterize exchange with the two-level system, exchange of L ₀ with {L _n } (R ₀ with {R _n }) and the phonon-induced decay of {L _n } and {R _n }. In addition to coherent oscillations with the frequency of the two-level system, Δ, and dissipative tunneling with a rate Δ²/πC ² (where C is the matrix element of the coupling of L ₀ and R ₀ with L _n and R _n ), a new regime appears where L-R transitions are induced by the partial recovery of the populations of L ₀ and R ₀ in each recurrence cycle due to synchronous transitions from reservoirs. These transitions induce repeating changes in the populations of the states of the two-level system (Loschmidt echo). The number and width of the echo components increase with the cycle number. Evolution becomes irregular because of the mixing of the contributions from pulses of the neighboring cycles, when the cycle number k exceeds the critical value k _c = π² C ². Unlike the populations, their cycle-average values remain regular at k ≫ k _c. When Δ ≪ πC ², the cycle-average populations oscillate with a frequency of ΔΩ/πC ² irrespective of mixing. The frequency of oscillations of the populations of the states {L _n } and {R _n } is approximately nΩ(Δ/2πC ²)², where Ω is the spacing between the neighboring levels of the reservoir and nΩ is the difference between the energies of the states L ₀ and L _n . The appearance of the mentioned low-frequency oscillations is due to the formation of collective states of the two-level system that are “dressed” by the reservoir. The predicted oscillations can be detected by femtosecond spectroscopy methods.     

Noncommutative electromagnetism as a large <Emphasis Type="Italic">N</Emphasis> gauge theory

We map noncommutative (NC) U(1) gauge theory on ℝ _C ^d ×ℝ _NC ²ⁿ to U(N→∞) Yang–Mills theory on ℝ _C ^d , where ℝ _C ^d is a d-dimensional commutative spacetime while ℝ _NC ²ⁿ is a 2n-dimensional NC space. The resulting U(N) Yang–Mills theory on ℝ _C ^d is equivalent to that obtained by the dimensional reduction of (d+2n)-dimensional U(N) Yang–Mills theory onto ℝ _C ^d . We show that the gauge-Higgs system (A _μ ,Φ ^a ) in the U(N→∞) Yang–Mills theory on ℝ _C ^d leads to an emergent geometry in the (d+2n)-dimensional spacetime whose metric was determined by Ward a long time ago. In particular, the 10-dimensional gravity for d=4 and n=3 corresponds to the emergent geometry arising from the 4-dimensional N=4{\mathcal{N}}=4 vector multiplet in the AdS/CFT duality. We further elucidate the emergent gravity by showing that the gauge-Higgs system (A _μ ,Φ ^a ) in half-BPS configurations describes self-dual Einstein gravity.     

Geometrical and electronic structures of CunC±, CunC2± (n = 1–5) clusters: A first-principles study

The geometrical and electronic structures of Cu_nC^±, Cu_nC₂^± (n =?1–5) clusters have been investigated using spin-polarized DFT calculations. There are much more differences in ground-state structures of Cu_nC^± (n =?2–5) and Cu_nC₂^± (n =?1–4) clusters. The planar structure plays a dominated role in Cu_nC₂^± (n =?1–5) clusters with two C atoms always bonding together, and leads to Cu clusters catalyzing carbon nanofibers effectively. The HOMO-LUMO energy gaps of Cu_nC^±, Cu_nC₂^± (n =?1–5) clusters show obviously even-odd oscillation. According to the fragmentation energy of neutral and charged Cu_nC, Cu_nC₂ (n =?1–5) clusters, we predict that the carbon nanofibers prepared in experiments are electropositive.     

Hydrogen-abstraction reactions of fully hydrogenated fullerene cages with the amino radical: a density functional study

We have applied density functional theory calculations to study the reactions of NH₂ + C_nH_n (n = 20, 40, 50, 60, 70 and 80). Due to the hard curvature in C₂₀ cage, the NH₂? + C₂₀H₂₀ → NH₃ + C₂₀H₁₉? reaction is nearly thermoneutral with a high potential barrier height. For the C_nH_n fulleranes with n > 20 the transition states appear earlier on the reaction paths, as can be anticipated for exothermic reactions. Using the spherical excess parameter, we distinguished different curvatures on the surfaces of fullerane cages. The reaction enthalpies ΔH°₂₉₈ and potential barrier heights ΔE^TS of the considered reactions indicate good correlation with the values of ?_i parameter, showing an upward trend with the curvature increasing at carbon sites. We have also investigated the H-abstraction of the chemical derivatives of the C₂₀H₂₀ cage (C₂₀H₁₉–CH₃, C₂₀H₁₉–CH₂CH₃ and C₂₀H₁₉–CH₂CH₂CH₃) in comparison to the corresponding isolated alkanes (CH₄, C₂H₆ and C₃H₈). Overall, it could be inferred that the H-abstraction from the primary and secondary C–H bonds of isolated alkanes could occur more easily than fullarane derivatives.     

态|Ψn(2)>q的广义非线性等阶N次方H压缩效应

构造了一种新型的多模叠加态|Ψ_n⁽²⁾>_q=C_n^(R)|{-iZ_j^*}>_q+C_n⁽⁰⁾|{O_j}>_q;并首次详细地研究了此量子态的等阶N次方H压缩特性.大量的计算和分析表明:态|Ψ_n⁽²⁾>_q是一种多模典型的非经典光场;还发现了"相似压缩"等现象.     

TDDFT study on electronic excitations and first hyperpolarizabilities of mixed-metal carbonyl clusters MonIr4-n(μ-CO)3(β5-Cp)n (n = 1,2,3)

A series of mixed-metal carbonyl clusters, Mo_nIr_4-n(μ-CO)₃(CO)_9-n(η⁵-Cp)_n (n?=?1, 2; Cp?=?C₅H₄Me, C₅HMe₄, C₅Me₅, C₅H₅), have been investigated using the TDDFT method. The results estimated the medium magnitude of the first static hyperpolarizabilities (β _tot ?～?2?×?10^?30esu) of these tetrahedral mixed-metal clusters, most of which originate from the intra-cluster charge transfer of the metal skeleton consisting of polar metal–metal interactions. No direct contributions of the Cp ligands to the relevant charge transfer were found, but the cooperative effect between the metal centres and Cp ligands impacts the β. Based on these studies a mixed-metal cluster Mo₃Ir(μ-CO)₃(CO)₇(η⁵-Cp)₂ was designed that exhibits enhanced first hyperpolarizability.     

Comparative Plasma Chemical Reaction Studies of CH4/Ar and C2Hm/Ar (m = 2,4,6) Gas Mixtures in a Dielectric Barrier Discharge

Plasma chemical reactions in CH4/Ar and C₂H_m/Ar (m = 2, 4, 6) gas mixtures in a dielectric barrier discharge at medium pressure (300 mbar) have been investigated. From mass spectrometry the production of H₂ and formation of larger hydrocarbons such as C_nH_m with up to n = 12 is inferred. Hydrogen release is most pronounced for CH₄ and C₂H₆ gas mixtures. Fourier Transform InfraRed (FTIR) spectroscopy reveals the formation of substituted alkane (sp³), alkene (sp²), and alkyne (sp) groups from the individual gases which are used in this work. Abundant formation of acetylene occurs from C₂H₄ and to a lesser extent from C₂H₆ and CH₄ precursor gases. The main reaction pathway of acetylene leads to the formation of large molecules via C₄H₂ and, eventually, to nano‐size particles. The experimental results are in reasonable agreement with simulations which predict a pronounced electron temperature and gas pressure dependency. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)