Rotational spectroscopy of DO2 by FIR LMR and millimeter-wave absorption

Trevor J. Sears, Gerald A. Takacs, Carleton J. Howard, Richard L Crownover, Paul Helminger, Frank C. De Lucia

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We report the measurement of approximately 50 rotational transitions in the DO2 radical between 230 and 2530 GHz by high-resolution millimeter-wave and far-infrared laser magnetic resonance spectroscopy. The radical was generated in the gas phase by the reaction of chlorine atoms and oxygen or discharged oxygen with deuterated methanol. The data were analyzed in conjunction with previously published high-resolution spectra of the molecule in the ground vibronic state in order to extract the best set of parameters in the effective Hamiltonian describing the molecule. The fine structure (spin-rotation) parameters derived in the present work were used together with those for HO2 [A. Charo and F. C. De Lucia, J. Mol. Spectrosc. 94, 426-436 (1982)] in order to determine all of the symmetry-allowed spin-rotation tensor components for the hydroperoxyl radical. The results cannot be interpreted in terms of contamination of the ground state wavefunction by the lowest lying A ̃2 A ́ state alone and information from quantum chemical calculations of spin-orbit matrix elements between the ground and higher excited states or additional experimental data involving higher excited electronic states are necessary before a complete rationalization of the results is possible.

Original languageEnglish (US)
Pages (from-to)103-120
Number of pages18
JournalJournal of Molecular Spectroscopy
Volume118
Issue number1
DOIs
StatePublished - 1986
Externally publishedYes

Fingerprint

Millimeter waves
millimeter waves
Ground state
Spectroscopy
Magnetic resonance spectroscopy
Oxygen
Hamiltonians
Molecules
Laser spectroscopy
Infrared lasers
Chlorine
Electronic states
Wave functions
Excited states
Chemical elements
spectroscopy
Tensors
Methanol
Orbits
Contamination

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Sears, T. J., Takacs, G. A., Howard, C. J., Crownover, R. L., Helminger, P., & De Lucia, F. C. (1986). Rotational spectroscopy of DO2 by FIR LMR and millimeter-wave absorption. Journal of Molecular Spectroscopy, 118(1), 103-120. https://doi.org/10.1016/0022-2852(86)90228-6

Rotational spectroscopy of DO2 by FIR LMR and millimeter-wave absorption. / Sears, Trevor J.; Takacs, Gerald A.; Howard, Carleton J.; Crownover, Richard L; Helminger, Paul; De Lucia, Frank C.

In: Journal of Molecular Spectroscopy, Vol. 118, No. 1, 1986, p. 103-120.

Research output: Contribution to journalArticle

Sears, TJ, Takacs, GA, Howard, CJ, Crownover, RL, Helminger, P & De Lucia, FC 1986, 'Rotational spectroscopy of DO2 by FIR LMR and millimeter-wave absorption', Journal of Molecular Spectroscopy, vol. 118, no. 1, pp. 103-120. https://doi.org/10.1016/0022-2852(86)90228-6
Sears, Trevor J. ; Takacs, Gerald A. ; Howard, Carleton J. ; Crownover, Richard L ; Helminger, Paul ; De Lucia, Frank C. / Rotational spectroscopy of DO2 by FIR LMR and millimeter-wave absorption. In: Journal of Molecular Spectroscopy. 1986 ; Vol. 118, No. 1. pp. 103-120.
@article{9c2e302dafe5493087047ab3d88bcc85,
title = "Rotational spectroscopy of DO2 by FIR LMR and millimeter-wave absorption",
abstract = "We report the measurement of approximately 50 rotational transitions in the DO2 radical between 230 and 2530 GHz by high-resolution millimeter-wave and far-infrared laser magnetic resonance spectroscopy. The radical was generated in the gas phase by the reaction of chlorine atoms and oxygen or discharged oxygen with deuterated methanol. The data were analyzed in conjunction with previously published high-resolution spectra of the molecule in the ground vibronic state in order to extract the best set of parameters in the effective Hamiltonian describing the molecule. The fine structure (spin-rotation) parameters derived in the present work were used together with those for HO2 [A. Charo and F. C. De Lucia, J. Mol. Spectrosc. 94, 426-436 (1982)] in order to determine all of the symmetry-allowed spin-rotation tensor components for the hydroperoxyl radical. The results cannot be interpreted in terms of contamination of the ground state wavefunction by the lowest lying A ̃2 A ́ state alone and information from quantum chemical calculations of spin-orbit matrix elements between the ground and higher excited states or additional experimental data involving higher excited electronic states are necessary before a complete rationalization of the results is possible.",
author = "Sears, {Trevor J.} and Takacs, {Gerald A.} and Howard, {Carleton J.} and Crownover, {Richard L} and Paul Helminger and {De Lucia}, {Frank C.}",
year = "1986",
doi = "10.1016/0022-2852(86)90228-6",
language = "English (US)",
volume = "118",
pages = "103--120",
journal = "Journal of Molecular Spectroscopy",
issn = "0022-2852",
publisher = "Academic Press Inc.",
number = "1",

}

TY - JOUR

T1 - Rotational spectroscopy of DO2 by FIR LMR and millimeter-wave absorption

AU - Sears, Trevor J.

AU - Takacs, Gerald A.

AU - Howard, Carleton J.

AU - Crownover, Richard L

AU - Helminger, Paul

AU - De Lucia, Frank C.

PY - 1986

Y1 - 1986

N2 - We report the measurement of approximately 50 rotational transitions in the DO2 radical between 230 and 2530 GHz by high-resolution millimeter-wave and far-infrared laser magnetic resonance spectroscopy. The radical was generated in the gas phase by the reaction of chlorine atoms and oxygen or discharged oxygen with deuterated methanol. The data were analyzed in conjunction with previously published high-resolution spectra of the molecule in the ground vibronic state in order to extract the best set of parameters in the effective Hamiltonian describing the molecule. The fine structure (spin-rotation) parameters derived in the present work were used together with those for HO2 [A. Charo and F. C. De Lucia, J. Mol. Spectrosc. 94, 426-436 (1982)] in order to determine all of the symmetry-allowed spin-rotation tensor components for the hydroperoxyl radical. The results cannot be interpreted in terms of contamination of the ground state wavefunction by the lowest lying A ̃2 A ́ state alone and information from quantum chemical calculations of spin-orbit matrix elements between the ground and higher excited states or additional experimental data involving higher excited electronic states are necessary before a complete rationalization of the results is possible.

AB - We report the measurement of approximately 50 rotational transitions in the DO2 radical between 230 and 2530 GHz by high-resolution millimeter-wave and far-infrared laser magnetic resonance spectroscopy. The radical was generated in the gas phase by the reaction of chlorine atoms and oxygen or discharged oxygen with deuterated methanol. The data were analyzed in conjunction with previously published high-resolution spectra of the molecule in the ground vibronic state in order to extract the best set of parameters in the effective Hamiltonian describing the molecule. The fine structure (spin-rotation) parameters derived in the present work were used together with those for HO2 [A. Charo and F. C. De Lucia, J. Mol. Spectrosc. 94, 426-436 (1982)] in order to determine all of the symmetry-allowed spin-rotation tensor components for the hydroperoxyl radical. The results cannot be interpreted in terms of contamination of the ground state wavefunction by the lowest lying A ̃2 A ́ state alone and information from quantum chemical calculations of spin-orbit matrix elements between the ground and higher excited states or additional experimental data involving higher excited electronic states are necessary before a complete rationalization of the results is possible.

UR - http://www.scopus.com/inward/record.url?scp=0002396111&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0002396111&partnerID=8YFLogxK

U2 - 10.1016/0022-2852(86)90228-6

DO - 10.1016/0022-2852(86)90228-6

M3 - Article

AN - SCOPUS:0002396111

VL - 118

SP - 103

EP - 120

JO - Journal of Molecular Spectroscopy

JF - Journal of Molecular Spectroscopy

SN - 0022-2852

IS - 1

ER -