title: Lone-pair interactions and photodissociation of compressed nitrogen trifluoride.
abstract: High-pressure behavior of nitrogen trifluoride (NF3) was investigated by Raman and IR spectroscopy at pressures up to 55 GPa and room temperature, as well as by periodic calculations up to 100 GPa. Experimentally, we find three solid-solid phase transitions at 9, 18, and 39.5 GPa. Vibrational spectroscopy indicates that in all observed phases NF3 remains in the molecular form, in contrast to the behavior of compressed ammonia. This finding is confirmed by density functional theory calculations, which also indicate that the phase transitions of compressed NF3 are governed by the interplay between lone‑pair interactions and efficient molecule packing. Although nitrogen trifluoride is molecular in the whole pressure range studied, we show that it can be photodissociated by mid-IR laser radiation. This finding paves the way for the use of NF3 as an oxidizing and fluorinating agent in high-pressure reactions.
authors.affiliation: Centre of New Technologies, University of Warsaw, 02-097 Warsaw, Poland.
authors.forename: D
authors.initials: D
authors.lastname: Kurzydłowski
authors.affiliation: Department of Biogeochemistry, Max Planck Institute for Chemistry, 55128 Mainz, Germany.
authors.forename: H B
authors.initials: HB
authors.lastname: Wang
authors.affiliation: Department of Biogeochemistry, Max Planck Institute for Chemistry, 55128 Mainz, Germany.
authors.forename: I A
authors.initials: IA
authors.lastname: Troyan
authors.affiliation: Department of Biogeochemistry, Max Planck Institute for Chemistry, 55128 Mainz, Germany.
authors.forename: M I
authors.initials: MI
authors.lastname: Eremets
mesh_terms: D005459:Fluorides / Q000737:chemistry* / Q000528:radiation effects*; D017672:Nitrogen Compounds / Q000737:chemistry* / Q000528:radiation effects*; D055668:Photochemical Processes; D011312:Pressure
chemical_list: D017672:Nitrogen Compounds; C534617:nitrogen trifluoride; D005459:Fluorides