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In the present study, dissociative electron attachment (DEA) measurements with gas phase HMX, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, C4H8N8O8, have been performed by means of a crossed electron-molecular beam experiment. The most intense signals are observed at 46 and 176 u and assigned to NO2(-) and C3H6N5O4(-), respectively. Anion efficiency curves for 15 negatively charged fragments have been measured in the electron energy region from about 0-20 eV with an energy resolution of ~0.7 eV. Product anions are observed mainly in the low energy region, near 0 eV, arising from surprisingly complex reactions associated with multiple bond cleavages and structural and electronic rearrangement. The remarkable instability of HMX towards electron attachment with virtually zero kinetic energy reflects the highly explosive nature of this compound. Substantially different intensity ratios of resonances for common fragment anions allow distinguishing the nitroamines HMX and royal demolition explosive molecule (RDX) in negative ion mass spectrometry based on free electron capture.

Helium nanodroplets are doped with SF(6), C(4)F(8), CCl(4), C(6)H(5)Br, CH(3)I, and I(2). Upon interaction with free electrons a variety of positively and negatively charged cluster ions X(+/-)He(n) are observed where X(+/-) = F(+/-), Cl(+/-), Br(+/-), I(+), I(2) (+), or CH(3)I(+). The yield of these ions versus cluster size n drops at characteristic sizes n(s) that range from n(s) = 10.2+/-0.6 for F(+) to n(s) = 22.2+/-0.2 for Br(-). n(s) values for halide anions are about 70% larger than for the corresponding cations. The steps in the ion yield suggest closure of the first solvation shell. We propose a simple classical model to estimate ionic radii from n(s). Assuming the helium density in the first solvation shell equals the helium bulk density one finds that radii of halide anions in helium are nearly twice as large as in alkali halide crystals, indicating the formation of an anion bubble due to the repulsive forces that derive from the exchange interaction. In spite of the simplicity of our model, anion radii derived from it agree within approximately 10% with values derived from the mobility of halide anions in superfluid bulk helium, and with values computed by quantum Monte Carlo methods for X(-)He(n) cluster anions.

Survival of the weakest: The existence of a new class of centrosymmetric radical cations in which H(2) bridges two identical main group elements was recently proposed in this journal by Uggerud and co-workers. By growing complexes inside helium nanodroplets at subkelvin temperatures, we obtained experimental evidence for the existence of the most weakly bound member of this class, He-H-H-He(+) (see picture), although in a metastable, electronically excited state.In a recent report, Uggerud and co-workers (A. Krapp et al., Chem. Eur. J. 2008, 14, 4028) proposed the existence of a new class of radical cations in which a dihydrogen bridges two identical main group elements. Upon electron impact ionization of helium nanodroplets doped with one or more H(2) molecules we observe various He(x)H(y) (+) cluster ions, including He(2)H(2) (+), which would belong to the proposed class of radical cations. Mass-analyzed kinetic energy scans reveal that the ion is metastable; it dissociates in the field-free region of the mass spectrometer. One reaction is into HeH(2) (+) + He with a low kinetic energy release of 15+/-4 meV. Surprisingly, another unimolecular reaction is observed, into HeH(+) + HeH (or He + H). The probability of this reaction is an order of magnitude higher, and the average kinetic energy release is four times larger. These findings suggest the presence of a metastable electronically excited state; they are consistent with the proposed linear, centrosymmetric ion structure of He-H-H-He(+).