Electronic structure of PCBM

We have studied the electronic structure of [6,6]-phenyl-C₆₁-butyric-acid-methyl-ester (PCBM) using synchrotron radiation photoelectron spectroscopy (PES) measurements and first-principles calculations. The PES spectrum of the entire occupied valence band is reported, which exhibits abundant spectral features from the Fermi level to ～24 eV binding energy. All the spectral features are broadened as compared with the cases of C₆₀. The reasons for the broadening are analysed by comparing the experimental data with the calculated energy levels and density of states. Special attention is paid to the analysis of the C₆₀ highest occupied molecular orbital (HOMO)-1 derived states, which can play a crucial role in the bonding at the interfaces of PCBM/polymer blenders or PCBM/electrodes. Besides the well-known energy level splitting of the C₆₀ backbone caused by the lowered symmetry, C 2p states from the side chain mix or hybridize with the molecular orbitals of parent C₆₀. The contribution of the O 2p states can substantially modify the PES spectrum.     

A Molecular Thermometer Based on the Delayed Fluorescence of C70 Dispersed in a Polystyrene Film

A new optical molecular thermometer, based on the thermally activated delayed fluorescence of C₇₀ dispersed in a polystyrene film, was developed. In the presence of oxygen, the fluorescence intensity of the C₇₀ film is essentially temperature independent in a wide range. In the absence of oxygen, however, the fluorescence intensity markedly increases with temperature. At room temperature (25°C), and after degassing the sample, the fluorescence intensity of C₇₀ increases 22 times, while at 100°C the fluorescence intensity is increased by 70 times. With our system, the very weak fluorescence of C₇₀ (Φ_F ≅ 5 × 10⁻⁴, in toluene) can be increased up to 91 times (up to an estimated maximum value Φ_F = 0.046). The estimate value of the singlet-triplet gap (29 kJ mol⁻¹) and the fluorescence lifetime (0.63 ns) of the C₇₀ in film are in agreement with the values reported in the literature for C₇₀ in solution. The values of the phosphorescence lifetime at room temperature (23 ms) and the quantum yield of triplet formation (0.989) were also determined. The system is completely reversible with respect to heating-cooling cycles.     

Features of the energy distribution of secondary particles upon the ion bombardment of graphite

The secondary emission of carbon atoms from the (0001) plane of graphite nanocrystallites bombarded with argon ions with energies of 1 and 10 keV and the incidence angle α = 45° is investigated. The unusual oscillating energy distributions of secondary C⁺ ions with main maxima E _max in the range of 40–60 eV and peaks corresponding to the energies E ₁ ≈ 20, 30, 70, 80, and 100 eV have been revealed. The C⁺ ion yield decreases, the energy spectrum increases, and the maximum E _max shifts to larger energies E ₁ with increasing emission angle (with respect to the normal to the surface). The secondary-ion emission from the (0001) face of graphite is numerically simulated with allowance for the charge exchange of secondary ions to obtain a qualitative explanation of the observed results.     

FePc与TiO2(110)及C60界面电子结构研究

基于C₆₀受体和有机分子给体的太阳能电池是目前非常重要的一个研究热点, 利用同步辐射真空紫外光电子能谱(SRUPS) 技术研究了酞菁铁(FePc)与TiO₂(110)及C₆₀的界面电子结构, 以及FePc与C₆₀分子混合薄膜的电子结构. SRUPS价带谱显示, FePc沉积在化学计量比与还原态两种不同的TiO₂(110)表面时, FePc分子的HOMO能级均随FePc厚度的变化发生了移动, 而在化学计量比的TiO₂(110)表面位移较大, 同时发生界面能带弯曲, 说明存在从有机层向衬底的电子转移. 在FePc/C₆₀和C₆₀/FePc界面形成过程中, FePc与C₆₀分子的最高占据分子轨道(HOMO)位移大小基本相同. 由界面能级排列发现, 在FePc与C₆₀的混合薄膜中, FePc分子的HOMO与C₆₀分子的最高占据分子轨道能级差较大, 这有利于提高器件开路电压, 改善器件性能.     

Electron energy loss spectra from polycrystalline Cr and Cr2O3 before and after surface reduction by Ar bombardment

Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr₂O₃ before and after surface reduction by 2 keV Ar⁺ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr₂O₃ exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar⁺ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr²⁺ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr₂O₃ surface exhibit features characteristic of both Cr⁰ and Cr₂O₃, indicating that Ar⁺ sputtering reduces Cr₂O₃. The fact that neither the surface- nor the bulk-plasmon features of Cr⁰ can be observed in the ELS spectra obtained from sputtered Cr₂O₃ while the loss features due to Cr⁰ interband transitions are clearly present indicates that Cr⁰ atoms form small clusters lacking a bulk metallic nature during Ar⁺ bombardment of Cr₂O₃.     

Optical and magneto-optical properties of the endohedral La@C82 crystal

The magneto-optical properties of solids are theoretically described by the circular dichroism (CD) and birefringence coefficient (θ). Using the Su-Schrieffer-Heeger (SSH) model in conjunction with the local field method, the optical dielectric tensor, CD and θ of the simple cubic phase of the La@C₈₂ and C₈₂ crystals are calculated. The results obtained from the La@C₈₂ and C₈₂ crystals are compared with those of the C₇₀ and C₆₀ crystals. It is shown that La@C₈₂ has a richer optical spectrum than C₈₂, C₇₀ and C₆₀. In the La@C₈₂ crystal, absorption bands are shown by spectrum in the 0.58 to 7.0?eV region with sharp structures in each band which indicate the localized molecular structure coupled with long-range crystalline order. Results show that the circular dichroism and birefringence coefficient of the La@C₈₂ crystal due to a single spin localized on the C₈₂ cage are very larger than those of the C₆₀, C₇₀ and C₈₂ crystals. Also, results show that the circular dichroism and birefringence coefficient of the C₈₂ crystal are similar to those of the C₆₀ and C₇₀ crystals.     

An investigation into allegations of double scattering in the carbon K-shell electron energy loss spectrum of acetylene

In several recent publications (R. G. Cavell and D. A. Allison, J. Chem. Phys., 69 (1978) 159; A. Barth et al., Chem. Phys., 46 (1980) 149) it has been suggested that the feature at 295.6 eV energy loss in the carbon K-shell spectrum of C₂H₂ may arise from double scattering (i.e., collisions of one electron with two acetylene molecules). The pressure-dependence of the carbon K-shell excitation spectrum of C₂H₂ has been examined by inelastic scattering of 2.5-keV electrons to investigate this possibility. The intensity of all features, including that at 295.6 eV, was observed to vary linearly with pressure, indicating that the spectral features arise only from single collisions.     

Total electron scattering cross section of C3F6O at the intermediate-energy region for developing an alternative insulation gas to SF6

Perfluoro methyl vinyl ether (C₃F₆O) is a promising alternative gas to SF₆ for switching applications in the power industry. We measured the total electron scattering cross section (TCS) of C₃F₆O in the intermediate energy region from 15 to 90 eV using a magnetized electron beam apparatus. The overall TCS values were less than 20.8 × 10⁻¹⁶ cm² within the measuring energy region. The measured and observed TCS exhibited some features, a steep increase before 30 eV, the highest value near 30 eV, and a gradual decrease after 30 eV. The total uncertainty was evaluated as 3.5–8.5%, depending on the incident electron energies. These first measurement data of C₃F₆O are useful for understanding both the discharging characteristics and identifying the insulation properties and arc-extinguishing.     

Theoretical study of mechanisms for NCO with CH3 reaction

A detailed computational study has been performed at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) level for the NCO with CH₃ reaction by constructing singlet and triplet potential energy surfaces (PES). The results show that the title reaction is more favorable for the singlet PES than the triplet PES. On the singlet PES, the dominant channel is the barrierless addition of the O or N atom to the C atom of the methyl group to form CH₃NCO (IM1) and CH₃OCN (IM2). On the triplet PES, the favorable channel is the barrierless addition of the N atom to the C atom of the methyl group to form an intermediate CH₃NCO (³IM2), which then undergoes a N–C bond scission process to give out CH₃N + CO.     

Crystal structure of solid C70

Detailed analysis of the room temperature X-ray powder diffraction data of pure solid C₇₀ is reported. C₇₀ prepared by slow evaporation from toluene solution adopts an hcp structure (space groupP6₃/mmc) witha=10·53(1) A andc=17·24(1) A. C₇₀ sublimed on to Si wafer adopts an fcc structure witha=14·89(1) A. The occurrence of both the hcp and fcc phases is rationalized in terms of cohesive energy calculations. Theoretical calculations of the diffraction pattern for the hcp structure, taking into account (a) orientational disorder amongst the molecules (b) presence of stacking faults and (c) a fraction of the sample to be amorphous/microcrystalline is seen to provide very good agreement with the experimental diffraction pattern.     

Resonance Energy Transfer in New Fullerene–Coumarin Diads

The fluorescence properties of new [60] and [70] fullerene–coumarin diads are studied. These diads were synthesized by covalently linking a coumarin dye to a fullerene (C₆₀ or C₇₀) by a cyclopropanation reaction. The absorption and fluorescence spectra, quantum yields and lifetimes of the diads are reported. The fluorescence quenching of the coumarin moiety by the fullerene was observed in all diads, indicating the occurrence of resonance energy transfer between the coumarin and fullerene moieties.     

Electron transmission and quantum current distribution of C<Subscript>70</Subscript> molecule

The characteristics of electron transmission through C₇₀ molecule bridge in which two atomic chain leads are connected to long-axis carbon atoms are investigated theoretically by using tight-binding approach based on the Green’s function with only one π orbital electron per carbon atom. Electron transmission through C₇₀ molecule from the input to the output terminal is obtained. From the spectrum, the switching feature of the electron transmission through C₇₀ is found, and the oscillation property based on the quantized level is explained. The quantum current distributions inside C₇₀ molecule bridge are calculated and simulated by the quantum current density theory based on Fisher-Lee formula at the energy point E = −0.2 eV, where the transmission spectrum shows a peak. The maximum and the minimum bond quantum currents are presented, and the reason why the currents are distributed nonuniformly is explained by the phase difference of the atomic orbits. The result shows that the currents at each atomic site agree with Kirchhoff quantum current conservation law. Supported by the National Key Basic Research Development Project (Grant No. 2003CB716204), the International Corporation Project of the Education Department of China (Grant No. 20050360563), the Key Laboratory of Advanced Photonic and Electronic Materials of Jiangsu (Grant No. BM2003202) and the State Key Laboratory of Solid State Microstructures of Nanjing University     

Luminescent silicon nanocrystal dots fabricated by SiCl4/H2 RF plasma-enhanced chemical vapor deposition

Luminescent nanocrystalline Si dots were fabricated directly on thermally grown SiO₂ at 120°C by conventional RF plasma-enhanced chemical vapor deposition using tetrachlorosilane, SiCl₄ and H₂. As-deposited Si dot exhibits photoluminescence (PL) in the visible region, consisting of two broad bands corresponding to photon energies of 1.38 and 1.48 eV. Storage in air enhances PL and shifts the PL peak energy to higher wavelengths for dots of diameter less than 10 nm. Fourier transform attenuated total reflection absorption spectroscopy (FTIR-ATR) study reveals that the spontaneous oxidation proceeds until saturation after 70 h at dot sizes of 3–5 nm. The relationship between PL intensity, blueshift of PL peak energy, and surface termination species during oxidation indicates that these changes are attributed to the increased density of radiative centers at the Si nanocrystal dot/SiO₂ interface and enhancement of the quantum confinement effect.     

The Auger electron spectrum of carbon suboxide (C3O2)

The high resolution KLL Auger electron spectrum of carbon suboxide (C₃O₂) in gas form, has been recorded. Assignments, assisted by intensity and energy calculations, are proposed for the peaks in the spectrum. A comparison is made with the oxygen Auger spectrum of CO. The ground state energy of the doubly charged C₃O₂ ion is found to be 29.7 eV.     

富勒烯衍生物苯基C71-丁酸甲酯的结构和电学性质第一性原理研究

使用B3LYP/6-31G（d）方法对有机太阳电池中作为电子受体材料的富勒烯衍生物苯基C₇₁-丁酸甲酯（［70］PCBM）的同分异构体进行了计算.PCBM与C₇₀通过六元环和六元环共用的CC双键加成得到的产物是热力学控制产物;通过五元环和六元环共用的C—C键加成得到的产物则是动力学控制产物.［70］PCBM与C₇₀的第一绝热电子亲和势很接近.PCBM对前线轨道贡献很小,［70］PCBM的最高占据分子轨道和最低未占据分子轨道（LUMO）的电子云主要分布在C₇₀笼上.PCBM提升了C₇₀的LUMO能级水平,有利于提高太阳电池的光电转换效率.自然布居分析表明,PCBM与C₇₀之间没有发生显著的电荷转移.所有的性质研究表明,PCBM基团并不涉及电池光电转换过程,但在调整C₇₀能级水平提高光电转换效率中发挥了重要作用. 关键词： 71-丁酸甲酯')" href="#">苯基C₇₁-丁酸甲酯 电子受体 结合能 第一绝热电子亲和势     

Many-body effect in the coincidence L3 and M3 photoelectron spectroscopy spectra of Cu metal

The coincidence L₃ and M₃ photoelectron spectroscopy (PES) main lines of Cu metal are calculated by a many-body theory. There is no peak-energy shift between the singles PES main line and the coincidence one. The asymmetric narrowing of the coincidence PES main line on the low kinetic energy (KE) side is very small. This is in accord with recent experimental findings. In Cu metal, the shakeup satellite intensity is small and the main-line satellite separation energy is much larger than the core–hole lifetime width. The interference via the final-state interaction is negligible. In the PES main line, the imaginary part of the self-energy by shakeup excitations, which is very small compared to the core–hole lifetime width, decreases very slowly in linear with photoelectron KE. The branching ratio of Auger decay of a single hole state then increases very slowly in linear with photoelectron KE so that the deviation of the coincidence PES main line from the singles one is very small. The 939 eV structure seen only in the coincidence L₃ PES spectrum of Cu metal is attributed to the enhancement of the inelastic peak of a smaller energy loss due to electrons of a smaller average emission depth measured in coincidence with the elastic Auger peak. The structure will not be enhanced in the singles PES spectrum. The background subtraction in the coincidence spectrum cannot be the same as that in the singles one. Such consideration is necessary before we can conclude about the asymmetric narrowing on the low KE side. A unique capability of APECS by which one can determine the photoelectron KE dependent part of the imaginary part of the self-energy is pointed out.     

Delayed ionisation of C70

A delayed ionisation experiment has been carried out on laser excited C₇₀ molecules. Ions and electrons are detected in coincidence to distinguish the ionisation of C₇₀ from that of C₆₈ molecules created by the dominant process, emission of C₂. From the time dependence of the C₇₀⁺ yield and the ratio to the C₆₈⁺ yield, we can deduce both the dissociation energy, E_d = 9.7 ±0.3 eV, and the pre–exponential factor, A_d = 1.7 ×10²⁰ s^-1, in the Arrhenius decay law for C₂ emission. The power of photon emission from neutral C₇₀ is also determined.     

Dielectric relaxation,ac and dc conductivities in the fullerenes C60 and C70

The complex conductivity in polycrystalline C₆₀ and C₇₀ has been investigated for frequencies 20 Hz≤ν≤10⁶ Hz and temperatures 10 K≤T≤750 K. The high-frequency dielectric constants ε_α= 2.6±0.1(C₆₀) and ε_∞= 4.6±0.1 (C₇₀) were deduced from these experiments. The observed low temperature relaxation process in C₆₀ fits well into the relaxation dynamics of the C₆₀ molecules as determined by many other experimental techniques operating on very different time scales. In addition to the study of the dipolar relaxation process, the dc and ac conductivities were determined. From the temperature dependence of the dc conductivities energy barriers of E_G=1.75±0.1 eV (C₆₀) and E_G=1.7±0.1 eV (C₇₀) were estimated. In C₇₀ we found indications for small polaron tunneling.     

SiX2(X=H，F)分子的结构与势能函数

应用QCISD/6-311++G(3df,3pd)和B3P86/6-311++G(3d2f)对SiH₂,SiF₂的结构进行了优化,优化出SiH₂分子的稳定构型为C_2v,电子态为¹A₁,其平衡核间距R_e=0.15149nm、键角∠HSiH=92.5025°、离解能为3.7098eV. SiF _{关键词： 2}')" href="#">SiH₂ 2')" href="#">SiF₂ 多体项展式理论 势能函数     

Density functional theory study of hydrogen storage on Ni-doped C59X (X = B,N) heterofullerene

ABSTRACT

Hydrogen storage reactions on Ni ? C₅₉X(X = B, N) heterofullerene are investigated by using the state-of-the-art density functional theory calculations. The Ni atom prefers to bind at the bridge site between two hexagonal rings, and can bind up to five hydrogen molecules with average adsorption energies of (?0.94, ?0.48, ?0.33, ?0.25 and ?0.20 eV) per hydrogen molecule for Ni ? C₅₉B, while (?1.20, ?0.60, ?0.41, ?0.28 and ?0.23 eV) per hydrogen molecule for Ni ? C₅₉N. With no metal clustering, the system gravimetric capacities are expected to be as large as 10.87 and 10.85 wt % for 5H₂NiC₅₉B?and 5H₂NiC₅₉N, respectively. While the desorption activation barriers of the complexes 1H₂ + C₅₉X?(X = B, N)?are outside the Department of Energy domain (?0.2 to ?0.6 eV), the desorption activation barriers of the complexes nH₂ + C₅₉X(X = B, N)(n = 2 ? 5) are inside this domain. The hydrogen storage of the irreversible 1H₂ + NiC₅₉X?(X = B, N) and reversible 2H₂ + NiC₅₉X?(X = B, N) interactions is characterised in terms of density of states and projected densities of states, pairwise and non-pairwise additivity, infrared, Raman, electrophilicity and molecular electrostatic potentials.