Toluene Cluster Formation in Laval Expansions: Nucleation and Growth.

ABSTRACT

Toluene cluster formation has been investigated in the postnozzle flows of Laval expansions at flow temperatures between ∼48 and 73 K, toluene number concentrations between ∼1013 and 1015 cm-3, and for growth times of up to ∼170 µs. The clusters were detected by soft ionization mass spectrometry to ensure minimum cluster fragmentation upon ionization. The optimum conditions were achieved with single-photon ionization using vacuum ultraviolet (VUV) photons of 13.3 eV energy and low fluences. The nature of the onset of toluene cluster formation hints at barrierless nucleation, which seems a likely scenario for the high supersaturations (>1019) of the present experiments. This contrasts with the onset behavior observed for propane in earlier studies, which suggested nucleation in the presence of a barrier. Subsequent cluster growth has been studied as a function of the growth time for various toluene partial pressures. Size-resolved growth data have been recorded for all cluster sizes from the dimer to aggregates composed of ∼2400 monomers (∼4.4 nm in size), revealing general trends in the growth behavior. The current experiments provide systematic size- and time-resolved data on cluster formation at high supersaturations as a possible benchmark for the understanding of cluster formation under such conditions.