skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV

Abstract

The electronic state spectroscopy of carbonyl sulphide, COS, has been investigated using high resolution vacuum ultraviolet photoabsorption spectroscopy and electron energy loss spectroscopy in the energy range of 4.0–10.8 eV. The spectrum reveals several new features not previously reported in the literature. Vibronic structure has been observed, notably in the low energy absorption dipole forbidden band assigned to the (4π←3π) ({sup 1}Δ←{sup 1}Σ{sup +}) transition, with a new weak transition assigned to ({sup 1}Σ{sup −}←{sup 1}Σ{sup +}) reported here for the first time. The absolute optical oscillator strengths are determined for ground state to {sup 1}Σ{sup +} and {sup 1}Π transitions. Based on our recent measurements of differential cross sections for the optically allowed ({sup 1}Σ{sup +} and {sup 1}Π) transitions of COS by electron impact, the optical oscillator strength f{sub 0} value and integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis. Subsequently, ICSs predicted by the scaling are confirmed down to 60 eV in the intermediate energy region. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of carbonyl sulphide in the upper stratosphere (20–50 km)

Authors:
 [1];  [2];  [3]; ;  [1]; ;  [4];  [5];  [6];  [7];  [8]; ;  [9]
  1. Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)
  2. (Japan)
  3. (United Kingdom)
  4. Department of Physics, Sophia University, Tokyo 102-8554 (Japan)
  5. Development and Marketing Department, New Products Development Division, Kanto Denka, Kogyo Co., Ltd., Chiyoda-ku, Tokyo 101-0063 (Japan)
  6. Shibukawa Development Research Laboratory, New Products Development Division, Kanto Denka Kogyo Co., Ltd., Shibukawa City, Gunma 377-8513 (Japan)
  7. Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom)
  8. ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Århus C (Denmark)
  9. Départment de Chimie, Université de Liège, Institut de Chimie-Bât. B6C, allée de la Chimie 3, B-4000 Liège 1 (Belgium)
Publication Date:
OSTI Identifier:
22416106
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; CARBONYLS; DIFFERENTIAL CROSS SECTIONS; ELECTRONS; ENERGY ABSORPTION; ENERGY-LOSS SPECTROSCOPY; EV RANGE; EXCITATION; GROUND STATES; INTEGRAL CROSS SECTIONS; LIFETIME; OSCILLATOR STRENGTHS; PHOTOLYSIS; SULFIDES; ULTRAVIOLET RADIATION

Citation Formats

Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt, Department of Physics, Sophia University, Tokyo 102-8554, Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA, Ferreira da Silva, F., Almeida, D., Hoshino, M., Tanaka, H., Mogi, D., Tanioka, T., Mason, N. J., Hoffmann, S. V., Hubin-Franskin, M.-J., and Delwiche, J. Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV. United States: N. p., 2015. Web. doi:10.1063/1.4907200.
Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt, Department of Physics, Sophia University, Tokyo 102-8554, Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA, Ferreira da Silva, F., Almeida, D., Hoshino, M., Tanaka, H., Mogi, D., Tanioka, T., Mason, N. J., Hoffmann, S. V., Hubin-Franskin, M.-J., & Delwiche, J. Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV. United States. doi:10.1063/1.4907200.
Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt, Department of Physics, Sophia University, Tokyo 102-8554, Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA, Ferreira da Silva, F., Almeida, D., Hoshino, M., Tanaka, H., Mogi, D., Tanioka, T., Mason, N. J., Hoffmann, S. V., Hubin-Franskin, M.-J., and Delwiche, J. Sat . "Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV". United States. doi:10.1063/1.4907200.
@article{osti_22416106,
title = {Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV},
author = {Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt and Department of Physics, Sophia University, Tokyo 102-8554 and Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA and Ferreira da Silva, F. and Almeida, D. and Hoshino, M. and Tanaka, H. and Mogi, D. and Tanioka, T. and Mason, N. J. and Hoffmann, S. V. and Hubin-Franskin, M.-J. and Delwiche, J.},
abstractNote = {The electronic state spectroscopy of carbonyl sulphide, COS, has been investigated using high resolution vacuum ultraviolet photoabsorption spectroscopy and electron energy loss spectroscopy in the energy range of 4.0–10.8 eV. The spectrum reveals several new features not previously reported in the literature. Vibronic structure has been observed, notably in the low energy absorption dipole forbidden band assigned to the (4π←3π) ({sup 1}Δ←{sup 1}Σ{sup +}) transition, with a new weak transition assigned to ({sup 1}Σ{sup −}←{sup 1}Σ{sup +}) reported here for the first time. The absolute optical oscillator strengths are determined for ground state to {sup 1}Σ{sup +} and {sup 1}Π transitions. Based on our recent measurements of differential cross sections for the optically allowed ({sup 1}Σ{sup +} and {sup 1}Π) transitions of COS by electron impact, the optical oscillator strength f{sub 0} value and integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis. Subsequently, ICSs predicted by the scaling are confirmed down to 60 eV in the intermediate energy region. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of carbonyl sulphide in the upper stratosphere (20–50 km)},
doi = {10.1063/1.4907200},
journal = {Journal of Chemical Physics},
number = 6,
volume = 142,
place = {United States},
year = {Sat Feb 14 00:00:00 EST 2015},
month = {Sat Feb 14 00:00:00 EST 2015}
}
  • The electronic state spectroscopy of perfluorocyclobutane (c-C{sub 4}F{sub 8}) has been investigated using high resolution vacuum ultraviolet (vuv) photoabsorption spectroscopy in the energy range 6.0-11 eV. The electron energy loss spectrum (EELS) was also recorded in the nonelectric dipolar interaction mode (100 eV incident energy, 10 deg. scattering angle) over the 8-14 eV energy-loss range and the excited states in the 11-14 eV spectral region have been observed. An He I photoelectron spectrum recorded between 11.0 and 19.8 eV is compared with earlier lower resolution results. This has allowed us to derive a more precise value of 12.291{+-}0.002 eV formore » the ground neutral state vertical ionization energy. All spectra presented in this paper represent the highest resolution data yet reported for perfluorocyclobutane, to the best of our knowledge. Ab initio calculations have been performed for helping in the assignment of the spectral bands for both neutral excited states and ionic states.« less
  • The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5–10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic statemore » spectroscopy of furfural over an extended energy range.« less
  • The highest resolution vacuum ultraviolet photoabsorption spectrum of ethyl formate, C{sub 2}H{sub 5}OCHO, yet reported is presented over the wavelength range 115.0–275.5 nm (10.75–4.5 eV) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series, observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Calculations have also been carried out to determine the ionization energies and fine structure of the lowest ionic state of ethyl formate and are compared with a newly recorded He(I) photoelectron spectrum (from 10.1 to 16.1 eV). Newmore » vibrational structure is observed in the first photoelectron band. The photoabsorption cross sections have been used to calculate the photolysis lifetime of ethyl formate in the upper stratosphere (20–50 km)« less
  • Normalized absolute differential and integral cross sections for electron-impact excitation of five optically-allowed singlet states, two known triplet states, and two unknown triplet-like states of N/sub 2/, lying in the energy-loss range 12.5--14.2 eV, have been determined by analysis of electron energy-loss data at incident electron energies of 40 and 60 eV. The range of scattering angles considered in this work was 5/sup 0/ to 138/sup 0/. The optically allowed transitions are to the b /sup 1/Pi/sub u/, c /sup 1/Pi/sub u/, c' /sup 1/..sigma../sub u//sup +/, o /sup 1/Pi/sub u/, and b' /sup 1/..sigma../sub u//sup +/ states and themore » known triplet excitations are to the F /sup 3/Pi/sub u/ and G /sup 3/Pi/sub u/ states. Cross sections for excitation to two unidentified triplet-like states at 13.155 and 13.395 eV were also obtained from the data analysis. The relationship of the generalized oscillator strength for the dipole-allowed states obtained from the present measurements to known optical oscillator strengths is discussed.« less
  • New data have been obtained about the singlet excited states of ammonia in the 5.5--11 eV energy range by electron energy loss spectroscopy. The 50 eV excitation spectrum has been analyzed with high energy resolution (15 meV) at several scattering angles ranging from 4/sup 0/ to 40/sup 0/. Some known vibrational progressions have been completed by new additional terms with high quantum numbers v'. The differential cross section for the five lowest energy singlet states have been measured at 50 eV impact energy as a function of the scattering angle. These data lead to discuss the classification of the Rydbergmore » series.« less