Rotranslational dynamics of confined water. II. Spectroscopic evidence of confinement effects on the far-infrared spectra of water isotopologues in argon and krypton matrices.

Water molecules trapped in rare gas matrices exhibit conspicuous shifts in their far-infrared (FIR), rotranslational spectral features compared with the corresponding transitions observed in the gas phase. These confinement-induced perturbations have been related not only to the quantization of translational motion but also to the coupling between the orientational and positional degrees of freedom: the rotation-translation coupling (RTC). As the propensity displayed by the nuclear spin isomers (NSI) of water to undergo interconversion in confinement is intimately related to how its nuclear spin degrees of freedom are coupled with those for intra- and intermolecular motions, confinement-induced RTC should also strongly impact the NSI interconversion mechanisms and rates.

Sign flipping of spontaneous polarization in vapour-deposited films of small polar organic molecules.

Films of polar molecules vapour-deposited on sufficiently cold substrates are not only amorphous, but also exhibit charge polarization across their thickness. This is an effect known for 50 years, but it is very poorly understood and no mechanism exists in the literature that can explain and predict it. We investigated this bulk effect for 18 small organic molecules as a function of substrate temperature (30-130 K).