Suppression of fragment contributions to mass-selected resonance enhanced multiphoton ionization spectra of van der Waals clusters

Abstract

A technique is described for suppressing the contribution due to fragmentation of higher mass clusters in mass-selected resonance enhanced multiphoton ionization spectroscopy of weakly bound van der Waals (vdW) clusters formed in a skimmed supersonic expansion. Suppression is achieved by ionizing upstream from the extraction region of a time-of-flight mass spectrometer and by using a delayed voltage pulse to extract the ions. Normally, spectra associated with a particular cluster ion, e.g., AB+n will contain contributions from fragments formed by the dissociation of higher mass clusters, e.g., AB+n+m. However, with upstream ionization and delay extraction, AB+n fragments formed by AB+n+m dissociation that have different kinetic energy and altered trajectories from the directly ionized AB+n clusters, are not extracted efficiently and are hence discriminated against in detection. The technique is demonstrated with the aniline–argon vdW complex.