RUI: Exploring Differences between Condensed Phase Photolysis and Radiolysis

Wellesley College, Wellesley Hills MA

Investigators

Abstract

With with award, the Chemical Structure, Dynamics, and Mechanisms (CSDM-A) Program of the Division of Chemistry is funding Professor Christopher Arumainayagam at Wellesley College to study chemical reactions that are driven by interactions with light and/or electrons. Dr. Arumainayagam has devised probes to study the composition of nanoscale thin films under ultrahigh vacuum conditions before and after irradiation by low-energy electrons or photons. These probes enable his team to observe and characterize the subtle but important chemical changes induced by irradiation. This important category of chemical reactions impacts low-temperature plasmas used in industrially important processes such as plasma etching; use of low-energy electrons instead of photons for highly selective bond dissociations; identification of tracer molecules associated with specific pathways for interstellar synthesis of complex organic molecules (COM); and the relative roles of electrons and photons in atmospheric processes. Involvement of women and minority undergraduate students in this research is planned to promote diversification of the STEM workforce. The work specifically seeks to assess the differences and similarities between reactions initiated by low-energy (< 8 eV) electrons and photons. Target systems include condensed-phase ammonia, water and methanol, each of which is investigated using post-irradiation temperature programmed desorption, post-irradiation infrared reflection absorption spectroscopy, and isothermal electron/photon-stimulated desorption. Electrons/photons with sub-ionization energies are used to avoid production of low-energy secondary electrons, thereby ensuring that fundamental differences between electron and photon irradiation are probed. Among the objectives of the research are: (i) to measure the effective cross-section for electron/photon-induced reaction and desorption, and to identify all of the electron/photon-induced reaction products; (ii) to study the dependence of the reaction cross-sections and yields on electron/photon fluence, incident electron/photon energy, and film thickness; and (iii) to determine if the products identified by post-irradiation temperature-programmed desorption are nascent radiolysis products. The studies are designed to establish whether electron-induced condensed phase reactions generate unique molecular species; and whether electrons are more effective than photons for initiating specific condensed phase reactions.