Spontaneous Decay of Highly-Charged Fullerene Ions C60Z+ and C58z+

Abstract

Using isotope-resolved, two sector field mass spectrometric techniques we have identified and investigated quantitatively the energetics and kinetics (in particular the kinetic energy release, KER) of the spontaneous decay reactions C_60–2m ^z+ → C_60-2m-p(z-1)+ ₊ C_p ⁺ with m = 0 or 1, z ranging from 3 to 6 and p = 2 and 4. The obtained KER results are not compatible with the properties expected for a single-step fissioning reaction as described by the liquid drop model. Therefore the present data had to be interpreted by a different fragmentation mechanism. This novel reaction sequence, termed auto charge transfer (ACT) reaction, is initiated by the statistically driven neutral C₂ (or C₄₎ evaporation followed by an electron transfer process from the receding C₂ (or C₄) fragment to the remaining highly-charged fullerene ion thereby leading finally to the two charged reaction products observed in the exit channel of the decay reaction. Moreover, in the case that a C₂ ⁺ loss from C₆₀z+ is occurring in the first field-free region we have been able to demonstrate that it is possible to observe in the second field-free region a subsequent C₂ evaporation from the C₅₈(z-1)⁺ fragment ion.     

Thermally Activated Decay Processes of Isolated Superhot C60 in Molecular Beams

We have studied thermally activated decay processes of an ensemble of isolated superhot C₆₀ molecules in molecular beams by several different methods. Highly vibrationally excited C₆₀ molecules in effusive or supersonic beams (with average vibrational energy of 10-20 eV) were generated in an all ceramic, two-stage high temperature nozzle source. the decay kinetics due to various decay processes of the initially canonical ensemble was followed by a mass spectrometric methods for a large range of initial temperatures (T_o=1100 - 1950 K). the processes studied are: (1) fragmentation (C₂ emission) of the neutral C₆₀ (2) C₂ emission from the C⁺₆₀ ions (3) black-body like radiative cooling, and (4) delayed electron emission. the experiments described here are: (a) Depletion of the integrated C₆₀ flux. (b) Analysis of C₆₀ time-of-flight distributions. (c) Dependence of electron impact induced ionization/ fragmentation of C₆₀ upon its initial thermal excitation, and (d) Thermal energy dependence of delayed electron emission. It is shown that thermal kinetics models using a single set of independently measured parameters uniquely reproduce all the experimental observations. the models take into account the different cooling processes and their time evolution. We analyze in detail the evolution of the initially canonical vibrational energy distribution during the flight time to the detector as it is gradually being distorted due to evaporative and radiative cooling mechanisms. It is concluded that the correct parameters to be used for describing the thermally activated decay kinetics of superhot C₆₀ are activation energy of E_o = 4.3 - 4.8 eV for the neutral fragmentation channel C₆₀ → C₅₈ + C₂ and E₁=4.0 - 4.3 for the ion fragmentation channel C⁺₆₀→ C⁺₅₈ + C₂, and corresponding pre-exponential factors of A_o = A₁ = 2.5 × 10¹³ sec^-1. the emissivity coefficient for black body like radiation was found to be ε = 4.5 × 10^-5.     

Ion Formation and Fragmentation in Gas-Phase Fast-Atom Bombardment Mass Spectrometry of C60

The observation of multiply-charged ions C₆₀^Z+ (z=1-4) and fragment ions (C₆₀ - C_2n)^z+ (z=1-4, n=1-12) has been reported using a new ionization/ collision technique, called gas-phase fast-atom bombardment with a high-energy (8 keV) helium beam.     

GROUP TRANSFER AND DIMERIZATION PROCESSES OF C60(CN)2 UNDER ATMOSPHERIC PRESSURE IONIZATION CONDITIONS

Neutral and anionic C₆₀(CN)₂ were investigated with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectrometry. It was observed that its anions underwent cyano- group and oxygen transfer, and dimerization processes in ESI conditions to form C₆₀(CN)₃H^-, C₆₀(CN)₂(OH₂)^-, [C₆₀(CN)₃H]^-₂, [C₆₀(CN)₂(OH₂)]^-₂ and [(C₆₀)₂(CN)₂(OH)]^-. Meanwhile, neutral C₆₀(CN)₂, for which no signal was observed in ESIMS, showed a base peak corresponding to C₆₀(CN)₂Cl^- in APCIMS spectra with CHCl₃ used as solvent, while only a molecular ion peak corresponding to C₆₀(CN)^-₂ was observed for the toluene solution of neutral C₆₀(CN)₂ in the same conditions. Possible mechanisms for group transfer and dimerization were proposed based on these observations.     

Magnetic Properties of Some Fullerene Compounds

Magnetic properties of some fullerene intercalation compounds are detailed. A few examples are presented including properties of 1) Acceptors: MoF₆ From magnetic measurements the existence of positively charged C₆₀ (C₆₀⁺) can be inferred 2) Donnors: Yb_xC₆₀ and Eu₃C₆₀ compounds. Magnetic properties of (Yb_xC₆₀) are dominated by crystal field effects. A high field magnetic transition (17 T at 4 K) occurs in Eu₃C₆₀ associated with a large hysteresis of the magnetization and relaxation effects. This complex magnetic behaviour is attribued to Eu²⁺.     

Laser Photolysis Study on Mechanism and Efficiency of Electron Transfer Between Fullerenes (C60 and C70) and Tetraselenafulvalenes

Efficient electron-transfer reactions from three kind of tetraselenafulvalenes (TSeF's) to photoexcited triplet state of C₆₀ or C₇₀ in polar solvents have been confirmed by transient absorption spectroscopy observing the decay of ³C₆₀*/³C₇₀* and rise of C₆₀^-•/C₇₀^-•. Growth of single crystal seems to be stimulated by laser irradiation of the solution containing C₆₀ and bis(ethylenedithio)tetraselena-fulvalene (BEDT-TSeF), in which C₆₀^-• was effectively formed.     

紫外光激发Ce3+掺YVO4蓝光发射性能研究

利用提拉法生长了YVO₄和掺2.0at% CeO₂(或Ce₂(CO₃)₃)的YVO₄: Ce³⁺晶体。样品的XRD测试表明Ce³⁺代替Y³⁺进入晶格, Ce³⁺的加入并没有影响YVO₄的晶格结构。XPS测试显示YVO₄: Ce³⁺晶体中Ce离子3d分裂为882.0、885.8、902.9、908.0和915.9 eV等5个峰, 峰位表明样品中铈离子是以Ce³⁺和Ce⁴⁺两种价态形式存在。YVO₄和YVO₄: Ce³⁺激发谱都呈现出260~360 nm宽带激发, 此激发带源于基质中VO₄^3-离子团的配体O到V的电荷迁移吸收。使用325 nm的紫外线激发时, 两种样品均可发出以440 nm 为中心的宽带蓝光,其中YVO₄发射峰应归属于VO₄^3-离子团中³T₂→¹A₁和³T₁→¹A₁跃迁; 而YVO₄: Ce³⁺的蓝光发射则来源于Ce³⁺的5d→4f 的跃迁。分析可知YVO₄: Ce³⁺中VO₄^3-的π轨道和Ce³⁺的电子波函数能有效地重叠, 使得VO₄^3-和Ce³⁺可通过交换作用有效地向Ce³⁺传递能量, 可大幅提高Ce³⁺的蓝光发射强度。实验结果显示YVO₄: Ce³⁺可作为UV-LED管芯激发的白光发光二极管用高亮度蓝色发光材料。     

Effects of Hexasulfobutylated C60 on the Thalamic Neurons in Neonatal Rat in vitro

The effects of hexasulfobutylated C₆₀ (FC₄S) on membrane potentials and currents were studied by tight-seal, whole-cell recording in thin slices of the neonatal rat thalamus. Silent neuron with resting membrane potentials of around -62.4 ± 0.7 mV was found in whole-cell current clamp recordings. Hexasulfobutylated C₆₀ depolarized the neuron by a concentration dependent manner. It also (1) prolonged the decay time constant of action potential and (2) decreased the threshold of the directly elicited action potentials of the neuron. Hexasulfobutylated C₆₀ did not alter the input resistance of the excitable membrane. In whole-cell voltage clamp studies, depolarizing command pulses from a holding potential of about -70 mV evoked a fast inward current followed by an outward current in the thalamic neurons. Hexasulfobutylated C₆₀ (30 - 100 μM) increased the total inward sodium current of the neuron, while hexasulfobutylated C₆₀ did not alter the outward potassium currents in all voltage steps tested. It was concluded that hexasulfobutylated C₆₀ (1) decreased the threshold of the action potential and (2) prolonged the decay time constant of the directly elicited action potential of the neonatal rat thalamic neurons. The effect may be closely associated with the Na⁺ current in thalamic neurons.     

An aqueous ZnCl2/Fe(bpy)3Cl2 flow battery with mild electrolyte

The kinetics of electrode reaction was investigated by cyclic voltammetry, and cyclic voltammograms show that the reversibility of the Fe(bpy)₃²⁺/Fe(bpy)₃³⁺ electrode reaction is better than that of the Zn/Zn²⁺ electrode reaction on the graphite disc. However, the Fe(bpy)₃²⁺ ion diffusion in electrolyte is subject to greater resistance than that of the Zn²⁺ ion one. The stability of the Fe(bpy)₃Cl₂ solution was investigated by UV–vis spectroscopy, and the performance of a mild redox flow battery employing ZnCl₂ and Fe(bpy)₃Cl₂ in the NaCl aqueous solution with various membranes as the separator was also investigated. It was found that the Celgard 3501 membrane cannot effectively prevent Fe(bpy)₃²⁺ ions from leaking into anolyte, leading to the rapid failure of the flow battery. Although the Nafion 115 membrane can be polluted by Fe(bpy)₃²⁺ ions, it is not invalidated. The Nafion 115 membrane shows good selectivity, which can avoid Fe(bpy)₃²⁺ ions from leakage into anolyte. The ZnCl₂/Fe(bpy)₃Cl₂ flow battery with the Nafion 115 membrane exhibits the capacity retention of 80% after 200 cycles.     

Spectroscopic Evidence for Anionic Coordination Complexes of the Transition Metals with C70 and the Higher Fullerenes C76, C78, C82, C84, C86, C90, and C92

The carbonylate anions [M(CO)₅]^- (M = Mn, Re), [Co(CO)₄]^-, [CpFe(CO)₂]^-, and [CpM(CO)₃]^- (M = Mo, W) react with C₇₀ via single electron transfer processes to give, respectively, the corresponding 17-electron, metal-centered radicals Co(CO)₄, M(CO)₅ (M = Mn, Re), CpFe(CO)₂, and CpM(CO)₃ (M = Mo, W) in addition to the radical anion C₇₀^-. In secondary thermal or photochemical processes, the metal-centered radicals Co(CO)₄ and M(CO)₅ (M = Mn, Re) combine with the C₇₀^- to form the new η²-C₇₀ complexes [Co(CO)₃(η²-C₇₀)]^- and [M(CO)₄(η²-C₇₀)]^-. However, the metal-centered radicals CpM(CO)₃ (M = Mo, W) require photolysis to react with C₇₀^- to form [CpM(CO)₂(η²-C₇₀)]^-, whereas neither thermolysis nor photolysis induces reaction between CpFe(CO)₂ and C₇₀^-. The photochemical reaction of [Mn(CO)₅]^- with a mixture of higher fullerenes known to contain at least C₇₆, C₇₈, C₈₄, C₈₆, and C₉₀ resulted similarly in the formation of the higher fullerene complexes [Mn(CO)₄(η²-C_n)]^- (n = 76, 78, 80, 82, 84, 86, 88, 90, 92, 96, and 98), all identified using electrospray mass spectrometry.     

The Form of Sulfur Impurity in Neutron Irradiated Commercial C60

By using SEM, SAED, HRTEM and XPD it was found that the unexpectedly high sulphur impurity in some commercial C₆₀ product readily reacts with C₆₀, during neutron irradiation producing the compound C₆₀S₁₆⁽³⁾ that can be regarded as a stable collecting form of the original undefined sulphur impurities.     

Solubility of Fullerenes C60 and C70 in Seven Normal Alcohols and Their Deduced Solubility in Water

The solubilities of C₆₀ and C₇₀ at 25°C in seven normal alcohols obey the relationship InY = a + bX + cX², where Y is solubility and X is the Hildebrand solubility parameter of the solvent. Extrapolation to the solubility parameter of water yields solubilities in water of 1.3'10^-11 (C₆₀) and 1.3'10^-10(C₇₀) ng/ml with an uncertainty of one order of magnitude.     

THE ELUSIVE C60S: THREE ATTEMPTED SYNTHESES

Results of semiempirical energy calculations suggested that a [6,6]-closed C₆₀S fullerene sulfide might be stable. Attempts were therefore undertaken to synthesize the compound by UV photolysis of C₆₀ in CS₂ and by the heating of mixtures of C₆₀ and S₈ to 325 and 400°C. Any sulfide, if formed, was present in undetectably small quantities. However, [¹²C₆₀³⁴S]^- ions were observed when a mixture of solid C₆₀ and elemental sulfur was analyzed by Laser Desorption Ionization Time-of-Flight mass spectrometry.     

C60 Films Formed by Ionized Cluster Beam Deposition: Structure and Doping by Ion Implantation

C₆₀ films were formed on a variety of substrates by ionized cluster beam (ICB) technique. Their structure was found to depend on the acceleration voltages and substrate. Then the Coo films were implanted by P⁺-ions with doses from 0—2×10¹⁴ ion/cm². The in situ measurement of electrical conductivity revealed an abrupt decrease of three orders in resistance. The temperature coefficient of resistivity of the P⁺-ion implanted C₆₀ film remained in a negative value.     

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)_x C₆₀Br₈ at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C₆₀ Brg. The strongest mode at 1464 cm^-1 in C₆₀Br₈ is red shifted to a doublet with peaks at 1414 and 1421 cm^-1, implying an average phonon softening Δω of -47 cm^-1. A comparison with the phonon softening of the corresponding A_g(2) mode in alkali-doped C₆₀ (Δω ~ - 36 cm^-1 for A₆C₆₀, A = K, Rb or Cs) suggests that 8 electrons are transferred per C₆₀Br₈ molecule in the charge transfer complex. The mode at 503 cm_--1 in C₆₀Br₈ is shifted upwards, similar to that in A₆ C₆₀ compounds.     

Modification of Polyimide by Energetic C60+ Ions

Thin polyimide foils were irradiated with 20 and 30 MeV C₆₀+ ions and then examined by FTIR. First changes in the FTIR spectra were observed at fluences as low as some 10⁹ cm^-2. The findings point at the onset of formation of new radiochemical reaction products for low fluences, and at polyimide destruction at higher fluences. It appears possible to scale different results on C_n⁺ (n = 1 to 60) single-atomic, cluster and fullerene ion irradiation with the total transferred energy density p_t = S_tΦt, where Φt is the cluster ion fluence and S_t is the total cluster stopping power in the polymer.     

EPR of Graphite and Fullerenes

Analysis of the EPR results for graphite and fullerenes has led to the development of a model for the g-factor in follerene based on the analogy between graphite and fullerene. Pressure dependence of g-factor in C₆₀ powder confirms the validity of this model. ¹³C hyperfine splitting of_a0.36 mT in pristine fullerene is also reported. The g-factors of C₆₀^-1 and C₆₀^-3 in a solution and in a different K°C₆₀ fullerides are presented. C₆₀⁺ⁿ states should be described by the spectroscopic splitting factor larger than that of a free spin.     

Electron Microscopic Investigations of Transformations from C60 to Diamond, Filament and Microcapillary

We report the transformation of C₆₀ into diamond by electron beam pulse annealing of flash evaporated films (at 10^-6 torr) of C,₆₀, or by direct evaporation of C₆₀ in helium (100 torr) atmosphere. The formation of filament and microcapillaries (tubulene-like structures) by electron beam annealing of the C₆₀ deposit is also reported.     

C1 C60F16O: A Fluorofullerene Ether Having Exceptionally Long Chromatographic Retention

From the product of fluorination of [60]fullerene with K₂PtF₆ at 470 °C, we have isolated a small quantity (ca. 0.5 mg) of C₆₀F₁₆O, an oxahomofluorofullerene (ether) of exceptionally long HPLC retention time (50% greater than any other known fluorofullerene). The ¹⁹F NMR spectrum consists of 16 main lines and 8 minor ones, due to C₆₀F₁₆O (a single isomer of C₁ symmetry) and C₆₀F₁₆, respectively. The presence of the latter (absent on initial isolation) indicates this ether to be relatively unstable, confirmed by the failure to obtain an EI mass spectrum. The empirical formula was therefore determined by MALDI-TOF mass spectrometry in the negative-ion mode, the laser fluence being carefully adjusted at the threshold of ion formation, whence the only observable signal corresponded to the molecular ion of C₆₀F₁₆O. At slightly higher laser fluence, the base peak of C₆₀F₁₆O^·- is accompanied by C₆₀F₁₆^·- and C₆₀F₁₅O^·-. Two closely similar structures (of similar calculated stabilities) are fully consistent with the NMR data. Calculated dipole moments and the exceptionally long retention HPLC retention times suggest that both C₆₀F₁₆ and C₆₀F₁₆O may be dimers.     

The Solid-State Mechanochemical Reaction of Fullerene C60

The solid-state mechanochemical reaction of fullerene C₆₀ by the use of a high-speed vibration milling technique has been applied to the nucleophilic addition of an organozinc reagent to C₆₀, [4+2] cycloaddition of C₆₀ with condensed aromatic hydrocarbons, 1,3-dipolar addition of C₆₀ with organic azides, and dimerization of C₆₀.