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We have studied the dependence of electron impact induced ionization and fragmentation of C60 molecules in effusive molecular beams upon the initial thermal excitation in the temperature range of 1190–1875 K, corresponding to an average vibrational energy of 10–20 eV. This is the largest energy range of parent molecule thermal excitation ever reported for electron-impact mass-spectrometric studies. The normalized curves of electron energy (Ee) dependent ion currents of C+60 and C+58 were measured and analyzed for the temperatures (T0) of 1190, 1435, 1570, 1695, and 1875 K. Similar measurements were done for C+2n (n=26–28) fragments for T0=1190 and 1875 K. We have developed an expression for the dependence of C+58 fragment ion current i58(Ee,T0), formed via the decay process C+60→C+58+C2, on electron energy and initial temperature. Using this expression and the strong temperature dependence observed, we have proposed a simple experimental method for estimating the energy deposition function—the probability density of vibrational excitation ε by an ionizing electron of energy Ee. The effective (apparent) value of maximum deposited energy was found to be εm(Ee)=Ee−E*, where E*=30±5 eV. Possible interpretations for this surprisingly low value are discussed. Comparing the experimental i58(Ee,T0) curves with the calculated ones over the range of Ee=30–80 eV we find that for T0≤1600 K, good agreement is obtained assuming that the C60 initial internal excitation is determined by the source temperature alone. For the higher temperature range 1600 K≤T0≤1900 K, we had to use a modified calculation taking into account radiative cooling and ensemble evaporative cooling processes along the molecular beam flight path. As a result, we have obtained an accurate simulation of the complete family of i58(Ee,T0) curves over all the temperature range measured, using a single set of independently measured physical quantities, and without any adjustable parameter. Uniqueness and sensitivity were thoroughly checked and demonstrated. The good agreement between experiment and calculation basically confirms our description of the underlying process and provides an additional support for the values of the independent physical parameters used. We have used maximum energy deposition parameter of E*=31 eV, an activation energy of E0=4.3–4.5 eV for the neutral fragmentation channel C60→C58+C2 and E1=4.0 eV for the ion fragmentation channel C+60→C+58+C2, and pre-exponential factors of A0=A1=2.5×1013 s−1. These values are very close to former ones obtained by us from analysis of time-of-flight distributions and integrated flux decay measurements of hot C60 molecular beams. Correspondence with other results reported in the literature is discussed and a two-step dissociation mechanism is proposed.

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Impact of fullerene ions (C(60)(-)) on a metallic surface at keV kinetic energies and under single collision conditions is used as an efficient way for generating gas phase carbide cluster ions of gold and silver, which were rarely explored before. Positively and negatively charged cluster ions, Au(n)C(m)(+) (n = 1-5, 1 ≤ m ≤ 12), Ag(n)C(m)(+) (n = 1-7, 1 ≤ m ≤ 7), Au(n)C(m)(-) (n = 1-5, 1 ≤ m ≤ 10), and Ag(n)C(m)(-) (n = 1-3, 1 ≤ m ≤ 6), were observed. The Au(3)C(2)(+) and Ag(3)C(2)(+) clusters are the most abundant cations in the corresponding mass spectra. Pronounced odd/even intensity alternations were observed for nearly all Au(n)C(m)(+/-) and Ag(n)C(m)(+/-) series. The time dependence of signal intensity for selected positive ions was measured over a broad range of C(60)(-) impact energies and fluxes. A few orders of magnitude immediate signal jump instantaneous with the C(60)(-) ion beam opening was observed, followed by a nearly constant plateau. It is concluded that the overall process of the fullerene collision and formation∕ejection of the carbidic species can be described as a single impact event where the shattering of the incoming C(60)(-) ion into small C(m) fragments occurs nearly instantaneously with the (multiple) pickup of metal atoms and resulting emission of the carbide clusters. Density functional theory calculations showed that the most stable configuration of the Au(n)C(m)(+) (n = 1, 2) clusters is a linear carbon chain with one or two terminal gold atoms correspondingly (except for a bent configuration of Au(2)C(+)). The calculated AuC(m) adiabatic ionization energies showed parity alternations in agreement with the measured intensity alternations of the corresponding ions. The Au(3)C(2)(+) ion possesses a basic Au(2)C(2) acetylide structure with a π-coordinated third gold atom, forming a π-complex structure of the type [Au(π-Au(2)C(2))](+). The calculation shows meaningful contributions of direct gold-gold bonding to the overall stability of the Au(3)C(2)(+) complex.

A method of generating effusive molecular beams of C60 with vibrational temperatures up to 2000 K is presented. Direct measurement of the thermal stability and fragmentation kinetics of C60 in the range of 1100–1970 K, on the milliseconds time scale, provides thermal rate constants k(T)=10–300 s−1 (for T=1720–1970 K, respectively) and activation energy of E0=4.0±0.3 eV.