Terahertz and mid-infrared spectroscopy of matrix-isolated clusters and matrix-sublimation ice of DO
Yamakawa, Koichiro ; Nasu, Hirokazu*; Suzuki, Natsumi*; Shimizu, Genki*; Arakawa, Ichiro*
We have established an apparatus for terahertz and mid-infrared spectroscopy in an ultrahigh vacuum and have measured absorption spectra of DO clusters trapped in solid Ar. To assign terahertz absorption peaks due to the DO dimer, trimer, and tetramer, the dependence of the spectrum on the annealing temperature and DO dilution was analyzed. The assignment was also examined by ab initio calculations with use of the ONIOM method, where flexibility of surrounding Ar atoms was systematically incorporated. We identified all of the intermolecular fundamentals of the dimer and those with significant intensities of the trimer and tetramer, whose structural symmetries were revealed to be broken down. After isolating the DO clusters in solid Ar, we sublimated only Ar atoms to leave behind matrix-sublimation ice, which was found to be amorphous- or crystal-like depending on the formation conditions: the dilution and sublimation-temperature. Since the crystallinity got higher with raising the dilution and sublimation-temperature, the diffusion of the DO monomer on the surface of sublimating solid Ar was found to be crucial to the crystallization of the sublimation ice.