Structural relaxation of formic acid and its interaction with water and Xe at cryogenic temperatures

The glass-liquid transition of the amorphous HCOOH films and the reorganization of hydrogen-bonds of HCOOH during interactions with adsorbed D2O and Xe have been investigated on the basis of temperature-programmed TOF-SIMS and TPD. On the as-deposited HCOOH film at 15 K, the physisorbed Xe atom permeates through pores and is trapped in the bulk during pore collapse upon heating. The hydrogen bonds of the HCOOH film are persistent up to 125 K as revealed from the interaction with the adsorbed D2O molecules. The translational molecular diffusion commences at 125 K and dewetting of the HCOOH film follows at 150 K. The Xe atom incorporated in the bulk of the HCOOH film desorbs at 150 K concomitantly with dewetting of the film. These phenomena can be explained in terms of the glass-liquid transition of formic acid and the slow evolution of fluidity in the supercooled liquid phase. (c) 2006 Elsevier B.V. All rights reserved.