Single Photon Ionization Mass Spectroscopy of Hydrogen Bonded and van der Waals Cluster Systems Using a Capillary Discharge Soft X-Ray Laser

Abstract

We report the first use of a soft x-ray laser in photochemistry studies. A 46.9 nm capillary discharge soft x-ray laser was used to study hydrogen bonded and van der Waals cluster systems. The study of van der Waals cluster formation and growth in the gas phase can contribute to the understanding of solvation processes, solvation dynamics, and the nucleation and growth of small clusters. The comparative investigation of water, methanol, and ammonia clusters is of importance because these clusters demonstrate a wide range of van der Waals interactions and hydrogen bonding: water clusters are very strongly and dominantly hydrogen bonded; methanol clusters somewhat less so; and ammonia clusters perhaps not at all. Sulfur dioxide is the major contributor to acid rain and a generator of soot. The process of SO2 and water forming acid rain has been studied for some time in order to determine the atmospheric mechanism for this environmental issue. Carbon dioxide is the major gas phase pollutant responsible for the “green house effect” of the atmosphere. Many experiments employing supersonic expansion coupled with mass spectroscopic detection have been conducted in order to study monomeric and clustered structure and behavior of each of these systems. Spectroscopic and photochemical properties of the systems should be related to cluster structure. However, one of the most serious problems in the investigation of the distribution of neutral hydrogen-bonded and van der Waals clusters is the fragmentation or the intra-cluster ion-molecule reactions to the protonated cluster ions. Electron Impact (EI) ionization usually suffers considerably from fragmentation of parent cluster ions on account of the large excess energies during the ionization process. Multiphoton ionization (MPI) processes result in the predissociation of the neutral clusters before ionization. Single photon ionization is a more “gentle” way to study hydrogen-bonded and Van der Waals clusters since less fragmentation of the parent cluster ions occurs compared to EI and MPI ionization. We have used the 26.5 eV from a desk-top size Ne-like Ar capillary soft xray laser to do chemical cluster dynamics studies. A single photon from this laser is sufficient to ionize any cluster, molecule, or, even He atoms.