The Absorption Spectrum of H2S Between 2150 and 4260 cm-1: Analysis of the Positions and Intensities in the First (2nu2, nu1, and nu3) and Second (3nu2, nu1 + nu2, and nu2 + nu3) Triad Regions
The two triad systems of hydrogen sulfide (2nu2, nu1, and nu3 near 4 µm and 3nu2, nu1 + nu2, and nu2 + nu3 near 2.7 µm) were analyzed using 14 spectra recorded at 0.0056 and 0.011 cm-1 resolution with the McMath Fourier transform spectrometer located at Kitt Peak National Observatory. Experimental upper state levels of H232S, H234S, and H233S were obtained from assigned positions (as high as J = 20 and Ka = 15 for the main isotope). These were fitted to the A-reduced Watson Hamiltonian to determine precise sets of rotational constants through J10 and up to nine Fermi and Coriolis coupling parameters. Intensities of the two H232S triads were modeled with rms values of 2.5%, using the transformed transition moment expansion with 19 terms for 568 intensities of the first triad and 11 terms for the 526 intensities of the second triad. The second derivatives of the dipole moment with respect to normal coordinates were estimated in Debye to be: 22µx = -0.004873 (90); 12µx = 0.01372 (30); and 23µz = 0.01578 (30). This confirmed that for hydrogen sulfide some of the second derivatives are larger than the first derivatives. The calculated line intensities were summed yielding integrated band strengths (in cm-2/atm at 296 K) as follows: 0.3315 for 2nu2, 0.4522 for nu1, 0.1201 for nu3, 0.0303 for 3nu2, 1.820 for nu1 + nu2, and 2.869 for nu2 + nu3. In addition, the hot band transitions were identified in both regions. Finally, a composite database of hydrogen sulfide line parameters was predicted for the 5- to 2.5-µm region. Copyright 1998 Academic Press.
Brown
LR
Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, California, 91109
Crisp
JA
Crisp
D
Naumenko
OV
Smirnov
MA
Sinitsa
LN
Perrin
A