Design and testing of an (inert) gas cell for in situ polarization modulation infrared reflection absorption spectroscopic (PM-IRRAS) measurements under specific atmospheres

Infrared reflection absorption spectroscopy (IRRAS) is a powerful surface-sensitive analytical technique to characterize the adsorbed molecules on metal surfaces down to (sub)monolayer coverage. In this paper, a new (inert) gas cell is presented that expands the scope of the commercially available Bruker PMA50 module. The cell is designed as a sample holder to measure thin films of molecules adsorbed on a metal substrate under a specific gaseous atmosphere. The dimensions of the cell are chosen in such a way that it can be transferred into a glovebox via the standard entrance port (Ø150 mm), allowing the investigation of air-sensitive molecules under an inert-gas atmosphere. The cell has two hose connections through which the gas atmosphere can be varied as desired. This also allows for studying the reactivity of the adsorbed structures toward the surrounding gas in situ and in a (potentially) time-dependent fashion. Furthermore, the metal substrate can be irradiated via an exposure window to investigate the influence of light on the adsorbed molecules and/or their reactivity. Using the polarization-modulation (PM-) IRRAS technique along with the described gas cell, an air-sensitive molybdenum(0) tricarbonyl complex adsorbed on an Au(111) surface is investigated. This complex reacts with molecular oxygen to the molybdenum(VI) trioxo analog, and this conversion is accelerated by irradiation with light of 365 and 440 nm.