Surface-induced reactions and dissociations of small acetone, acetonitrile and ethanol cluster ions: competitive chemical reactions, dissociation mechanisms and determination of dissociation energy

Using a recently commissioned tandem mass spectrometer system, BESTOF, we have carried out systematic investigations (using also deuterated molecules) on the interaction of various molecular cluster ions (including stoichiometric acetone and acetonitrile cluster ions and protonated ethanol cluster ions) with a hydrocarbon-covered stainless steel surface. Besides observing competitive chemical reactions for the stoichiometric cluster ions driven by the energy transfer in the surface collision (intra-cluster reactions versus surface H-atom pick-up reactions), we were able to see clear evidence that unimolecular dissociation kinetics determines the production of the observed decay patterns in collision energy-resolved mass spectra (CERMS). From characteristic shifts in these CERMS we can deduce corresponding binding energies, i.e., {D}((CD₃CN)₂⁺ - CD₃CN) = 0.66 eV, {D}((C₂H₅OH)₂H⁺ - C₂H₅OH) = 0.95 eV, and for the protonated dimer {D}((C₂H₅OH)H⁺ - C₂H₅OH) = 1.6 eV. The first value is in good agreement with values currently calculated using the B3LYP (Becke-Lee-Yang-Parr) density functional and the 6-311G(d, p) basis set, the latter values are in good agreement with values derived earlier from thermochemical data.

Moreover, in the case of the protonated ethanol cluster ion, it is possible to arrive at a single (universal) breakdown graph for the trimer composed of data derived from monomer, dimer and trimer CERMS. This can be achieved by renormalizing the energy scale in the CERMS for the monomer, dimer and trimer ions (taking into account the conversion from translational to internal energy and assuming that the clusters behave like a statistical ensemble with the corresponding degrees of freedom).