Collision-induced dissociation evidence for charge separation and “ball-and-chain” propagation in the addition of 1-butene to C 60 2+

The collision-induced dissociation of the adduct ions C₆₀(C₄H₈) ₂ ²⁺ and C₆₀(C₄H₈) ₃ ²⁺ formed by sequential reactions of C ₆₀ ²⁺ with 1-butene has been investigated by using a selected-ion flow tube (SIFT) apparatus. Experiments at 295 ± 2 K in 0.35 ± 0.02 torr of helium indicated that C ₆₀ ²⁺ adds at least five molecules of 1-butene in a sequential fashion with rates that decrease with the number of molecules added. Collision-induced dissociation experiments in which the downstream sampling nose cone of the SIFT was biased with respect to the flow tube indicated that the adduct ions C₆₀(C₄H₈) ₂ ²⁺ and C₆₀(C₄H₈) ₃ ²⁺ dissociate into C ₆₀ ^·+ and (C₄H₈) ₂ ^·+ and (C₄H₈) ₃ ^·+ , respectively. These observations provide evidence for the occurrence of charge separation in the derivatization of C₆₀ dications and support the “ball-and-chain” mechanism first proposed by Wang et al. in 1992 for the sequential multiple addition of 1,3-butadiene to C ₆₀ ²⁺ and C ₇₀ ²⁺ .     

Coincidence studies of collisionally induced fission of C 60 2+

A direct measurement of collisionally induced fission of C ₆₀ ²⁺ has been performed. We have measured coincidences between various charged fragments resulting from collisions between C ₆₀ ²⁺ and He atoms. The measurements show that C ₆₀ ²⁺ not only emits C₂ units but also breaks up into larger, singly charged parts. In this paper, we report on coincidences between C _n ⁺ (2≦n≦9) and C _m ⁺ (42≦m≦48) fragment ions.     

Preparation and some properties of ionic salts of C 60 − and C 60 2− fullerides with phthalocyanine cations

Ionic fullerides of C ₆₀ ^? and C ₆₀ ^2? with the silicon phthalocyanines cations were obtained in the reaction of PcSi(OH)₂ with fullerene C₆₀ in the presence of KOH in DMSO or in xylene and THF with the addition of 15C5 crown ether. The fullerides were characterized by electron absorption, ¹H NMR and electron spin resonance spectra, and their reaction with O₂ and CF₃COOH were carried out.     

Gas-phase reactions between O−. and C6H5F: On the acidity of fluorobenzene and 1,4-difluorobenzene

The gas-phase reactions of negative ions (O^-., NH ₂ ^? , C₂H₅NH^?, (CH₃)₂N^?, C₆H ₅ ^t- , and CH₃SCH ₂ ^? ) with fluorobenzene and 1,4-difluorobenzene have been studied with Fourier transform ion cyclotron resonance mass spectrometry. The O^?. ion reacts predominantly by (1) proton abstraction, (2) formal H ₂ ^+. abstraction, and (3) attack on an unsubstituted carbon atom. In addition to these processes, attack on a fluorine bearing carbon atom yielding F^? and C₆H₄FO^? ions occurs with 1,4-difluorobenzene. Site-specific deuterium labeling reveals the occurrence of competing 1,2-, 1,3-, and 1,4-H ₂ ^+. abstractions in the reaction of O^?. with fluorobenzene. Attack of the O^?. ion on the 3- and 4-positions in fluorobenzene with formation of the 3- and 4-fluorophenoxide ions, respectively, is preferred to reaction at the 2-position, as indicated by the relative extent of loss of a hydrogen and a deuterium atom in the reactions with labeled fluorobenzenes. The NH ₂ ^? , C₂H₅NH^?, (CH₃)₂N^?, C₆H ₅ ^? , and CH₃SCH ₂ ^? anions react with fluoroberuene and 1,4-difluorobenzene only by proton abstraction. The relative importance of H⁺ and D⁺ abstraction in the reaction of these anions with labeled fluorobenzenes indicates that the 2-position in fluorobenzene is more acidic than the 3- and 4-positions, suggesting that the literature value of the gas-phase acidity of this compound (ΔH _acid ^o = 1620 ± 8 kJ mol^?1) refers to the former site. Based on the occurrence of reversible proton transfer between the CH₃O^? ion and 1,4-difluorobenzene, the ΔH _acid ^o of this compound is redetermined to be 1592 ± 8 kJ mol^?1.     

Electron impact ionization and dissociation of neutral and charged fullerenes

Three different types of electron impact ionization experiments have been performed, involving neutral and charged C₆₀ and C₇₀. 1) We have determined absolute partial ionization cross sections for formation of parent ions C ₆₀ ^z+ and C ₇₀ ^z+ in charge states up to z = 4, and of singly and multiply charged fragments of size n ≥ 44 and n ≥ 50 from C₆₀ and C₇₀ neutral precursors, respectively. 2) Previous appearance energy measurements of C₇₀ have been improved and extended to z = 5; ionization energies are found to depend linearly on the charge state of the precursor, in agreement with theoretical predictions. 3) A beam of mass selected C ₆₀ ²⁺ has been crossed with an intense electron beam; the induced reactions (fragmentation, post- ionization, and dissociative post-ionization) have been analyzed.     

Charge transfer in collisions involving multiply charged C60 molecules

Electron capture in collisions of C ₆₀ ²⁺ and C ₆₀ ³⁺ molecular ions with atomic and molecular gases has been studied at impact energies around 100 keV. The cross-section dependence on the target-ionization potentials is discussed, and a simple over-barrier model is evoked to explain the energy dependences. The cross sections for endothermic processes are discussed in the light of a simple two-state model, and a general understanding of their behaviour is obtained.     

The mass-to-charge ratio scale

Increases in the capacity for accurately measuring the mass-to-charge ratio of specific gas-phase ions justify the reconsideration and standard definition of the gas-phase mass-to-charge ratio scale and the clearly denned connection of that scale to condensed phases. We propose that the chemical mass standard for solids and the gas phase be based upon the mass of carbon-12 buckminsterfulierene (¹²C₆₀). The mass-to-charge ratio scale in the gas phase would be based upon the mass of gas-phase ¹²C₆₀, the mass of the electron, and the electron charge in atomic units. As mass measurement accuracy improves, corrections to this mass-to-charge ratio standard are anticipated for the vaporization energy of the 12C60 molecule and its ionization potential or electron affinity. We propose that the positive ion scale be set by the mass-to-charge ratio of ¹²C ₆₀ ⁺ as (+)719.9994514±0.0000004 u per electron charge. We propose that the negative ion mass scale be set by the mass-to-charge ratio of ¹²C ₆₀ ^? as (?)720.0005484±0.0000004 u per electron charge.     

Distribution of mass and averaged internal energy of fullerenes produced in arc-discharge ion source

In this work, the decay rate of fullerene ion beams as well as its dependence on the flight time from standard plasma type ion source has been studied. We have performed direct measurements of the decay probability of each fullerene ion (n=44 to 70) using two energy analyzers. The experimental results are well accounted for in terms of the concept of evaporating ensemble for the behavior of fullerenes in the continuous arc-discharge ion source. The obtained individually different internal energy distributions for fullerenes from C ₄₄ ⁺ to C ₆₈ ⁺ are for the first time presented.     

Surface-Induced dissociation from a liquid surface

Mass-selected projectile ions in the tens of electronvolt energy range undergo surface-induced dissociation upon collision with a liquid perfluorinated polyether (PFPE) surface. The efficiency of translational-to-vibrational (T-V) energy transfer is similar to that observed for a fluorinated self-assembled monolayer (SAM) surface. The thermometer ion W(CO)^’ was used to detenrrine an average T-V conversion efficiency of 18% in the collision energy range of 30–50 eV. The surface can be bombarded for several hours without displaying any change in the scattered ion products. Ion-surface reactions occur with some projectiles and are analogous to those seen with the fluorinated SAM surface. For example, WF _? ⁺ (m=1–5) and W(CO)_nF _? ⁺ (n=1–2, m=1–2) are generated upon collisions of W(CO) ₆ ⁺ with the PFPE liquid surface. The ion-surface reactions observed suggest that F atoms and/or CF₃ groups are accessible for reaction while the oxygen atoms lie below the outermost surface layer. Chemical sputtering of the liquid surface also occurs and yields common fluorocarbon fragment ions, including CF ₃ ⁺ , C₂F ₅ ⁺ , and C₃F ₇ ⁺ and the oxygenated product CFO⁺. The liquid surface is remarkably free of hydrocarbon impurities. Collisions of the pyrazine and benzene molecular ions, both probes for hydrocarbon impurities, resulted in very little protonated pyrazine or protonated benzene.     

Bimetallic cluster cations ejected from a liquid metal ion source: Li-Na and Li-Mg

Cluster ions of alloys (Li-Na, Li-Mg) have been produced by a liquid metal ion source (LMIS), and analyzed by mass spectrometry. For the Li-Na system, bimetallic clusters with various compositions were formed, and dominant bimetallic species were Na₂Li⁺, NaLi⁺, NaLi ₂ ⁺ and NaLi ₈ ⁺ with this sequence of ion intensity. These clusters are systems containing 2 or 8 valence electrons except for NaLi⁺. For the Li-Mg, observed bimetallic clusters were limited to only three species (MgLi⁺, MgLi ₂ ⁺ and Mg₂Li⁺), but unexpectedly small multiply charged homonuclear clusters, Mg ₂ ²⁺ and Mg ₃ ²⁺ , were observed.     

Isomerization of linear C3H 3 + in its reaction with acetylene,and collisional stabilization of the [C5H 5 + ]* collision complex in a quadrupole ion trap mass spectrometer

The isomerization of linear C₃H ₃ ⁺ in its reaction with acetylene to cyclic C₃H ₃ ⁺ was studied with a quadrupole ion trap mass spectrometer. The reaction of linear C₃H ₃ ⁺ with ¹³C₂H₂ shows that isomerization takes place via a [C₅H ₅ ⁺ ]^* activated complex that is unstable relative to disproportionation back into the cyclic and linear forms of C₃H ₃ ⁺ and acetylene. The formation of carbon-13 labeled cyclic and linear C,Hi indicates that isomerization involves skeletal exchange. Collisional stabilization of the [C₅H ₅ ⁺ ]^* collision complex was achieved at a helium pressure of approximately 1 mtorr.     

On the stability of Pb n m+ -clusters

The stability of multiply charged Pb _n ^m+ -clusters (n ≤ 3;m=0, 1, 2) was studied by solving exactly for the valencep-electrons a many body Hubbard-like Hamiltonian with intra- and interatomic Coulomb interactions. Particularly we obtain that Pb ₃ ²⁺ has a metastable ground state, in which Pb ₃ ²⁺ has isosceles shape (bond lengthR=3.2 Å, bond angle θ=124°) and a positive binding energyE _B =3.4 eV. The activation barrier against dissociation into Pb ₂ ⁺ + Pb⁺ is 0.13 eV, yielding a very long lifetime. This is in agreement with recent experiments [1] in which the lifetime of Pb ₃ ²⁺ was determined to be at least 10^?6 s. Comparison with self consistent Hartree-Fock calculations shows that the metastability of Pb ₃ ²⁺ is due to electronic correlations within the paramagnetic ground state.     

Investigation of the initial reactions of the Calcote mechanism for soot formation

The first three reactions of the Calcote mechanism for soot formation, that is, C₃H ₃ ⁺ +C₂H₂→C₅H ₅ ⁺ , C₅H ₅ ⁺ →C₅H ₃ ⁺ H₂, and C₅H ₃ ⁺ +C₂H₂→C₇H ₅ ⁺ , have been studied based on chemi-ions withdrawn directly from a premixed methane-oxygen flame by supersonic molecular beam sampling. The first reaction is reversible and involves the formation of a specific encounter complex sensitive to pressure and ion kinetic energy. The second reaction appears to require large amounts of internal energy in the C₅H ₅ ⁺ ion to proceed. The third reaction is reversible; however, in contrast to the initiating reaction, the C₅H ₃ ⁺ ion formed from the [C₇H ₅ ⁺ ]* complex exhibits a much lower reactivity. The conclusions are based on ion-molecule reactions as well as collision activation mass spectrometry of isolated chemi-ions. In addition, the product distributions as functions of pressure and ion kinetic energy were studied.     

Electronic transitions in C60 and its ions

The electronic spectrum of C₆₀ is calculated using quantum mechanical methods. The first allowed transition in C₆₀ is calculated at an energy of 3.5 eV and with an oscillator strength of 0.09. Several transitions are found at higher energies with comparatively strong oscillator strengths, the strongest one being at 5.78 eV (λ=214 nm). The calculated energy level diagram of C₆₀ is also used to predict wavelengths for transitions in C ₆₀ ⁺ and C ₆₀ ^? . A comparison is made with some recently observed diffuse interstellar bands at 1180 nm and 1320 nm, which have been speculated to originate from C ₆₀ ⁺ .     

Metastable and collision-induced fragmentation studies of all C4H12Si+ isomers; a systematic study of structure-reactivity relations

Metastable ion (MI) and collision-induced dissociation (CID) mass spectra have been recorded and compared for all nine C₄H₁₂Si^+. isomers. The (Me)₄Si^+., t-BuSiH ₃ ^+. , s-BuSiH ₃ ⁺ , and (Me)₂EtSiH^+. isomers have unique MI and CID mass spectra. The MI mass spectra, including the kinetic energy release values, of (Me)(i-Pr)SiH ₂ ^+. and (Me)(n-Pr)SiH ₂ ^+. are identical, which implies isomerization. MI data also suggest that a fraction of the n-BuSiH ₃ ^+. ions rearrange into branched (Me)₂EtSiH^+. ions and a fraction of the n-BuSiH ₃ ^+. ions rearrange into branched s-BuSiH ₃ ^+. ions. A comparison with the isomeric C₅H ₁₂ ^+. pentanes reveals a crucial difference: H₂ loss occurs for n-BuSiH ₃ ^+. , i-BuSiH ₃ ^+. , s-BuSiH ₃ ^+. , (Me)(n-Pr)SiH ₂ ^+. , (Me)(i-Pr)SiH ₂ ^+. , and Et₂SiH ₂ ^+. , but not for any of the C₅Hi ₁₂ ^+. isomers. Generation of four- or five-membered silicon containing rings is suggested for H₂ loss from the C₄H₁₂Si^+. silanes.     

Delayed emission of electrons from C60 following energetic impact against graphite

The yield of C ₆₀ ⁺ ions reflected from the surface of graphite is found to be a bimodal function of the energy of impact. Below 140 eV (6 km/s), the yield decreases with energy and the scattering time-of-flight peak is sharp. Above 170 eV, the yield increases, but the peak is broad and asymmetric, corresponding to delayed electron emission from an impact-heated, neutralized cluster. There is also evidence for fragmentation to C₅₈ and C₅₆. The emission process may be analogous to that reported for scattered C ₆₀ ^? . Application of statistical rate theory to either observation (C ₆₀ ^± ) gives an estimated 25–30 percent transfer of impact energy into cluster internal modes. The decreasing yield at highest energies (>400 eV) may result from adhesion processes (C₆₀-surface bonding) that could also account for the absence of delayed electron emission in C₆₀-silicon collisions.     

Influence of the organic layer thickness in (Metal-Assisted) secondary ion mass spectrometry using Ga+ and C 60 + projectiles

This article investigates the influence of the organic film thickness on the characteristic and molecular ion yields of polystyrene (PS), in combination with two different substrates (Si, Au) or gold condensation (MetA-SIMS), and for atomic (Ga⁺) and polyatomic (C ₆₀ ⁺ ) projectile bombardment. PS oligomer (m/z ～ 2000 Da) layers were prepared with various thicknesses ranging from 1 up to 45 nm on both substrates. Pristine samples on Si were also metallized by evaporating gold with three different thicknesses (0.5, 2, and 6 nm). Secondary ion mass spectrometry was performed using 12 keV atomic Ga⁺ and C ₆₀ ⁺ projectiles. The results show that upon Ga⁺ bombardment, the yield of the fingerprint fragment C₇H ₇ ⁺ increases as the PS coverage increases and reaches its maximum for a thickness that corresponds to a complete monolayer (～3.5 nm). Beyond the maximum, the yields decrease strongly and become constant for layers thicker than 12 nm. In contrast, upon C ₆₀ ⁺ bombardment, the C₇H ₇ ⁺ yields increase up to the monolayer coverage and they remain constant for higher thicknesses. A strong yield enhancement is confirmed upon Ga⁺ analysis of gold-metallized layers but yields decrease continuously with the gold coverage for C ₆₀ ⁺ bombardment. Upon Ga⁺ bombardment, the maximum PS fingerprint ion yields are obtained using a monolayer spin-coated on gold, whereas for C ₆₀ ⁺ , the best results are obtained with at least one monolayer, irrespective of the substrate and without any other treatment. The different behaviors are tentatively explained by arguments involving the different energy deposition mechanisms of both projectiles.     

Optical response of cesium coated C60

Photoabsorption spectra are reported for Cs _n ⁺ and C₆₀Cs_n ⁺ + clusters for n=40, 60, 120 and 310. The spectra were obtained by heating the mass selected clusters in a beam by means of photoabsorption until they evaporated metal atoms. The resulting mass loss was observed in a time-of-flight mass spectometer. The plasmon-like resonance in pure Cs clusters shifts to lower energies with decreasing cluster size. The collective electronic excitations in clusters containing C₆₀ are split in energy as would be expected for fullerene molecules coated with layers of metal.     

Nucleophilic assistance in methane activation by superelectrophiles with halogen-centered cationic sites

Simulation of fragments of potential energy surface for systems CH₄ + CBr ₃ ⁺ , CH₄ + CBr ₃ ⁺ AlBr ₄ ^? , CH₄ + CCl ₃ ⁺ AlCl ₄ ^? , and CH₄ + CCl ₃ ⁺ Al₂Cl ₇ ^? was performed by DFT-B3LYP and DFT-PBE methods. The important role of nucleophilic assistance in methane halogenation by these superelectrophiles was confirmed. These reactions occur with a synchronous hydride transfer from methane to the electrophile within the cyclic transition states in linear C-H-C fragment of the rings and a generation of a C-Hlg bond between the carbon atom of the arising methyl group and the halogen atom of the electrophile. The nucleophilic assistance from the unshared electron pair of this halogen atom provides the lowering of the potential barriers to methane halogenation by complexes CBr ₃ ⁺ AlBr ₄ ^? , CCl ₃ ⁺ AlCl ₄ ^? , and CCl ₃ ⁺ Al₂Cl ₇ ^? to the values of the order of 20 kcal mol^?1. These essential features of the mechanism of methane halogenation are independent of the halogen nature and are retained on going from the model electrophiles to the real ones.     

Ion-molecule reactions and collision-activated dissociation of C4H 4 +. isomers: A case study in the use of the MS3 capabilities of a pentaquadrupole mass spectrometer

Isomeric C₄H ₄ ^+. radical cations vinylacetylene (a), butatriene (b), methylene cyclopropene (c), and the nonaromatic cyclobutadiene (d), generated, respectively, from the neutral precursors 3-butyn-1-ol (1), 1,4-dichloro-2-butyne (2), benzene (3), and 7,8-benzotricyclo [4.2.2.0^2,5]deca-3,7,9-triene (4), undergo diagnostically different ion-molecule reactions with allene, isoprene, furan, and thiophene. It is speculated that adducts are generated by [2 + 2] cycloadditions with the first reagent and [4 + 2] Dials-Alder cycloadditions with isoprene, furan, and thiophene. The initially formed cycloaddition adducts fragment rapidly, isomerize, or undergo further addition of neutral reagent to yield a complex set of products. With a pentaquadrupole mass spectrometer, MS³ experiments that employ three stages of ion mass analysis are used to help elucidate the ion-molecule reactions and to distinguish the isomeric C⁴H ₄ ^+. ions. Among these experiments, the reaction intermediate spectrum reveals the nature of the intermediates connecting the reactant to a selected product while the sequential product spectrum provides mechanistic and structural information on the adducts and other ion-molecule products. The unique combination of ion-molecule reactions with collision-activated dissociation employed here provides valuable information on the chemistry of ionized cyclobutadiene, including its proclivity to undergo [2 + 2] and [4 + 2] cyc1oadditions.