Amorphous solid water films: transport and guest-host interactions with CO2 and N2O dopants.
Guest-host interactions have been examined experimentally for amorphous solid water (ASW) films doped with CO2 or N2O. The main diagnostics are Fourier transform infrared (FTIR) spectroscopy and temperature programmed desorption (TPD). ASW films deposited at 90 K are exposed to a dopant, and the first molecules that attach to a film enter its bulk until it is saturated with them. Subsequent dopant adsorption results in crystal growth atop the ASW film. There are distinct spectral signatures for these two cases: LO and TO vibrational modes for the crystal overlayer, and an easily distinguished peak for dopant molecules that reside within the ASW film. Above 105 K, the dopant surface layer desorbs fully. Some dopants residing within the ASW film remain until 155 K, at which point the ASW-to-crystalline-ice transition occurs, expelling essentially all of the dopant. No substantial differences are observed for CO2 versus N2O. It is shown that annealing an ASW film to 130 K lowers the film's capacity to include dopants by a factor of approximately 3, despite the fact that the ASW spectral feature centered at approximately 3250 cm(-1) shows no discernible change. Sandwiches were prepared: ASW-dopant-ASW etc., with the dopant layer displaying crystallinity. Raising these samples past 105 K resulted in the expulsion of essentially all of the crystalline dopant. What remained displayed the same spectral signature as the molecules that entered the bulk following adsorption at the surface. It is concluded that the adsorption sites, though prepared differently, have a lot in common. Dangling OH bonds were observed. When they interacted with a dopant, they underwent a red shift of approximately 50 cm(-1). This is in qualitative agreement with studies that have been carried out with weakly bound binary complexes. As a result of this study, a fairly complete, albeit qualitative, picture is in place for the adsorption, binding, and transport of CO2 and N2O in ASW films.