Hot Bands in Overtone Absorption Transitions: High Temperature Spectra

Abstract

The laser photoacoustic spectra of the 4v sub N-H and 4v sub C-H overtones of pyrrole, the 5v sub c-H of methyl isocyanide and acetonitrile, the 5v sub c-H and 6v sub C-H of isobutane, and the 6v sub c-H of cyclohexane were measured at temperatures up to 140 C (T sub 140) and compared to the room temperature (T sub rt) spectra. Hot bands were identified by their temperature dependence in pyrrole, methyl isocyanide and isobutane. From the change in the relative intensities of the hot band to the main band going from T sub rt to T sub 140, the wavenumbers of the thermally populated states were 405+/-80, 410+/- 80 and 208+/-40 /cm for pyrrole, isobutane and methyl isocyanide, respectively. These values compare well to the bending motion frequencies in these molecules. Large red shifts of the hot bands from the main peak were observed, as expected for high overtone transitions due to large anharmonicities. The anharmonic constants determined from these shifts are -25 /cm for the N-H in pyrrole and - 20 /cm for the C-H in methyl isocyanide and isobutane. In the case of the N-H absorption the hot band was completely separated from the transition. In the C-H overtone spectra these hot band absorptions were not separated and result in an apparent increased width of the overtone transition.

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Document Details

Document Type
Technical Report
Publication Date
Mar 17, 1993
Accession Number
ADA262213

Entities

People

  • Deanne Snavely
  • Salah Hassoon

Organizations

  • Bowling Green State University

Tags

DTIC Thesaurus Topics

  • Absorption
  • Absorption Spectra
  • Alkanes
  • Chemical Synthesis
  • Chemistry
  • Dye Lasers
  • Energy Bands
  • Frequency
  • High Temperature
  • Lasers
  • Low Temperature
  • Molecular Beams
  • Quantum Numbers
  • Spectra
  • Spectroscopy
  • United States
  • Vibrational Spectra

Fields of Study

  • Physics

Readers

  • Organic Chemistry
  • Spectroscopy.

Technology Areas

  • Directed Energy
  • Directed Energy - Lasers