Temperature and pressure dependence of line widths and integrated absorption intensities for the O-2 a(1)Delta(g)-X-3 Sigma(-)(g) (0,0) transition

Citation
Sm. Newman et al., Temperature and pressure dependence of line widths and integrated absorption intensities for the O-2 a(1)Delta(g)-X-3 Sigma(-)(g) (0,0) transition, J PHYS CH A, 104(42), 2000, pp. 9467-9480
Citations number
65
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
10895639 → ACNP
Volume
104
Issue
42
Year of publication
2000
Pages
9467 - 9480
Database
ISI
SICI code
1089-5639(20001026)104:42<9467:TAPDOL>2.0.ZU;2-7
Abstract
The electric-dipole forbidden a(1)Delta (g) - X(3)Sigma (-)(g) (0,0) band o f gas-phase O-2 has been studied in absorption at wavelengths around 1.27 m um using Fourier transform spectroscopy and a long-path absorption cell. Ex periments were conducted at temperatures of 294, 243, and 200 K and at pres sures in the range 140-750 Torr. Both pure O-2 and a mixture of 21% O-2/79% N-2 were studied, and line widths, integrated line intensities, and integr ated absorption intensities (AIs) for the (0,0) vibrational band were measu red. Integrated AIs were found to be independent of temperature, pressure, and gas composition, and the recommended value for the vibrational band fro m the current study is S-int = 3.210(15) x 10(-24) cm molecule(-1) (1 sigma error) for pure O-16(2), corresponding to an Einstein A-coefficient of A = 2.256(10) x 10(-4) s(-1). The effect of including other oxygen isotopomers is to increase the integrated AI value for this origin band to S-int = 3.2 26(15) x 10(-24) cm molecule(-1) Widths of individual spectroscopic lines d ecrease with increasing molecular rotational quantum number. The temperatur e dependence of Lorentzian line width components, gamma (T) (fwhm), is well represented by the expression gamma (T) = gamma (294K)(T/294 K)(-0.85). Th e effects of pressure broadening of lines by N-2 are indistinguishable from those for pure O-2 at the same temperature and pressure.