Local mode effects in the absorption spectrum of H2S between 10 780 and 11330 cm(-1)

The absorption spectrum of H2S (1159 lines) has been recorded between 10 78 0 and 11 330 cm(-1) by intracavity laser absorption spectroscopy (ICLAS). A s a result of the increase of sensitivity of ICLAS over previous Fourier tr ansform investigations in the same spectral region, the number of experimen tal energy levels of the (40(+), 1) and (40(-), 1) local mode states ((212) and (311) in normal mode notation) has been triplicated for the main isoto pic species H-2 S-32 (198 compared to 62). Moreover, 112 energy levels of H -2 S-34 and 25 energy levels of H-2 S-33, present in natural abundance in t he sample, could also be determined. Three rotational levels of the (30(+/- ), 3) local mode pair of dark states ((132) and (231) in normal mode notati on) of H-2 S-32 could also be observed through extra lines borrowing their intensities via resonance interactions with line-partners of the dominant b ands. The (40(+), 1) and (40(-), 1) local mode states form a degenerate loc al mode pair, with the same rotational structure for the two components. Th e observed energy levels were reproduced by an effective Hamiltonian includ ing the (40(+/-), 1) and (30(+/-), 3) interacting local mode pairs. This Ha miltonian was applied either in the C-2 nu or C-s symmetry groups leading t o an rms deviation of 0.0058 and 0.0068 cm(-1) respectively, comparable to the experimental accuracy (0.0028 cm(-1)). The degeneracy of the rotational structure of the (40(+/-), 1) pair is unaffected by the interaction with t he nearby (30(+/-), 3) local mode states. On the contrary, an additional in teraction with dark states lifts in some cases this degeneracy. The same ef fective Hamiltonian with scaled parameters was successfully used to reprodu ce the energy levels of the H-2 S-33 and H-2 S-34 isotopic species. Finally , the extremely weak 3 nu (1) + 3 nu (2) band of H-2 S-32 at 11 097.161 cm( -1) could also be detected leading to the determination of 70 levels of the corresponding (21(+), 3) upper state ((330) in normal mode notation). The integrated intensities have been estimated for the bands corresponding to t he (40+, 1) and (40-, 1) upper states. A total of six transformed dipole mo ment parameters were derived from the measured line intensities allowing to simulate very satisfactorily the observed spectrum. The transition moment relative to the (40-, 1) upper state is found about twice as large as the o ne relative to the (40(+), 1) state. (C) 2001 Academic Press.