An ion mobility mass spectrometer coupled with a cryogenic ion trap for recording electronic spectra of charged, isomer-selected clusters.

Infrared and electronic spectra are indispensable for understanding the structural and energetic properties of charged molecules and clusters in the gas phase. However, the presence of isomers can potentially complicate the interpretation of spectra, even if the target molecules or clusters are mass-selected beforehand. Here, we describe an instrument for spectroscopically characterizing charged molecular clusters that have been selected according to both their isomeric form and their mass-to-charge ratio. Cluster ions generated by laser ablation of a solid sample are selected according to their collision cross sections with helium buffer gas using a drift tube ion mobility spectrometer and their mass-to-charge ratio using a quadrupole mass filter. The mobility- and mass-selected target ions are introduced into a cryogenically cooled, three-dimensional quadrupole ion trap where they are thermalized through inelastic collisions with an inert buffer gas (He or He/N2 mixture). Spectra of the molecular ions are obtained by tagging them with inert atoms or molecules (Ne and N2), which are dislodged following resonant excitation of an electronic transition, or by photodissociating the cluster itself following absorption of one or more photons. An electronic spectrum is generated by monitoring the charged photofragment yield as a function of wavelength. The capacity of the instrument is illustrated with the resonance-enhanced photodissociation action spectra of carbon clusters (Cn +) and polyacetylene cations (HC2nH+) that have been selected according to the mass-to-charge ratio and collision cross section with He buffer gas and of mass-selected Au2 + and Au2Ag+ clusters.

Electronic spectra of positively charged carbon clusters-C2n + (n = 6-14).

Electronic spectra are measured for mass-selected C2n +(n = 6-14) clusters over the visible and near-infrared spectral range through resonance enhanced photodissociation of clusters tagged with N2 molecules in a cryogenic ion trap. The carbon cluster cations are generated through laser ablation of a graphite disk and can be selected according to their collision cross section with He buffer gas and their mass prior to being trapped and spectroscopically probed. The data suggest that the C2n +(n = 6-14) clusters have monocyclic structures with bicyclic structures becoming more prevalent for C22 + and larger clusters. The C2n + electronic spectra are dominated by an origin transition that shifts linearly to a longer wavelength with the number of carbon atoms and associated progressions involving excitation of ring deformation vibrational modes. Bands for C12 +, C16 +, C20 +, C24 +, and C28 + are relatively broad, possibly due to rapid non-radiative decay from the excited state, whereas bands for C14 +, C18 +, C22 +, and C26 + are narrower, consistent with slower non-radiative deactivation.