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Title: Lone-pair interactions and photodissociation of compressed nitrogen trifluoride

High-pressure behavior of nitrogen trifluoride (NF{sub 3}) 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 NF{sub 3} 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 NF{sub 3} 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 NF{sub 3} as an oxidizing and fluorinating agent in high-pressure reactions.
Authors:
 [1] ;  [2] ; ;  [3] ;  [3] ;  [4]
  1. Centre of New Technologies, University of Warsaw, 02-097 Warsaw (Poland)
  2. (Germany)
  3. Department of Biogeochemistry, Max Planck Institute for Chemistry, 55128 Mainz (Germany)
  4. (Russian Federation)
Publication Date:
OSTI Identifier:
22420038
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 6; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMMONIA; DENSITY FUNCTIONAL METHOD; INFRARED SPECTRA; LASER RADIATION; MOLECULES; NITROGEN FLUORIDES; PHASE TRANSFORMATIONS; PHOTOLYSIS; SOLIDS; SPECTROSCOPY