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Title: Infrared spectroscopy of HOOO and DOOO in {sup 4}He nanodroplets

Abstract

The HOOO hydridotrioxygen radical and its deuterated analog (DOOO) have been isolated in helium nanodroplets following the in situ association reaction between OH and O{sub 2}. The infrared spectrum in the 3500-3700 cm{sup -1} region reveals bands that are assigned to the {nu}{sub 1} (OH stretch) fundamental and {nu}{sub 1}+{nu}{sub 6} (OH stretch plus torsion) combination band of the trans-HOOO isomer. The helium droplet spectrum is assigned on the basis of a detailed comparison to the infrared spectrum of HOOO produced in the gas phase [E. L. Derro, T. D. Sechler, C. Murray, and M. I. Lester, J. Chem. Phys. 128, 244313 (2008)]. Despite the characteristic low temperature and rapid cooling of helium nanodroplets, there is no evidence for the formation of a weakly bound OH-O{sub 2} van der Waals complex, which implies the absence of a kinetically significant barrier in the entrance channel of the reaction. There is also no spectroscopic evidence for the formation of cis-HOOO, which is predicted by theory to be nearly isoenergetic to the trans isomer. Under conditions that favor the introduction of multiple O{sub 2} molecules to the droplets, bands associated with larger H/DOOO-(O{sub 2}){sub n} clusters are observed shifted {approx}1-10 cm{sup -1} tomore » the red of the trans-H/DOOO {nu}{sub 1} bands.« less

Authors:
; ;  [1]
  1. Department of Chemistry, University of Georgia, Athens, Georgia 30602 (United States)
Publication Date:
OSTI Identifier:
22099102
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 137; Journal Issue: 18; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; ABSORPTION SPECTROSCOPY; COOLING; DEUTERIUM COMPOUNDS; DROPLETS; HELIUM; HELIUM 4; INFRARED SPECTRA; ISOMERS; RADICALS; VAN DER WAALS FORCES

Citation Formats

Raston, Paul L., Liang Tao, and Douberly, Gary E. Infrared spectroscopy of HOOO and DOOO in {sup 4}He nanodroplets. United States: N. p., 2012. Web. doi:10.1063/1.4764298.
Raston, Paul L., Liang Tao, & Douberly, Gary E. Infrared spectroscopy of HOOO and DOOO in {sup 4}He nanodroplets. United States. doi:10.1063/1.4764298.
Raston, Paul L., Liang Tao, and Douberly, Gary E. Wed . "Infrared spectroscopy of HOOO and DOOO in {sup 4}He nanodroplets". United States. doi:10.1063/1.4764298.
@article{osti_22099102,
title = {Infrared spectroscopy of HOOO and DOOO in {sup 4}He nanodroplets},
author = {Raston, Paul L. and Liang Tao and Douberly, Gary E.},
abstractNote = {The HOOO hydridotrioxygen radical and its deuterated analog (DOOO) have been isolated in helium nanodroplets following the in situ association reaction between OH and O{sub 2}. The infrared spectrum in the 3500-3700 cm{sup -1} region reveals bands that are assigned to the {nu}{sub 1} (OH stretch) fundamental and {nu}{sub 1}+{nu}{sub 6} (OH stretch plus torsion) combination band of the trans-HOOO isomer. The helium droplet spectrum is assigned on the basis of a detailed comparison to the infrared spectrum of HOOO produced in the gas phase [E. L. Derro, T. D. Sechler, C. Murray, and M. I. Lester, J. Chem. Phys. 128, 244313 (2008)]. Despite the characteristic low temperature and rapid cooling of helium nanodroplets, there is no evidence for the formation of a weakly bound OH-O{sub 2} van der Waals complex, which implies the absence of a kinetically significant barrier in the entrance channel of the reaction. There is also no spectroscopic evidence for the formation of cis-HOOO, which is predicted by theory to be nearly isoenergetic to the trans isomer. Under conditions that favor the introduction of multiple O{sub 2} molecules to the droplets, bands associated with larger H/DOOO-(O{sub 2}){sub n} clusters are observed shifted {approx}1-10 cm{sup -1} to the red of the trans-H/DOOO {nu}{sub 1} bands.},
doi = {10.1063/1.4764298},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 18,
volume = 137,
place = {United States},
year = {2012},
month = {11}
}