Journal of Physical Chemistry A, Vol.117, No.50, 13236-13248, 2013
New Analysis of the 1.13 and 7.14 Bands of HNO3 in the 7.6 mu m Region
A new line position analysis of the v3 and v, bands of nitric acid (FINO3) at 1326.186 and 1303.072 cm(-1) together with its associated interacting bands is presented. The 31 and 41 energy levels were obtained, from an extended analysis of high-resolution Fourier transform spectra recorded at Giessen in the 7.6 pm region. The energy levels of 31 and 41 upper states of nitric acid are strongly interacting with those of the 93, 62, 5191, and 7181 dark states centered at 1288.899, 1289.46, 1341.05, and 1343.78 cm-1, respectively. Informations on these perturbing dark states were achieved through previous partial investigations of hot bands in high-resolution Fourier transform spectra recorded at 22 pm in Giessen (for 31192v9 and 3119-115), at 12 pm in Denver (for 3v(9)-v(9)), and at 11 pm in Orsay (for v(s)+v(9)-v(9)). The energy levels calculation accounts for the various Fermi, anharmonic, A-type, B-type, and C-type Coriolis resonances, which couple together the {62,93,41,31,5191,7.181} interacting energy levels. For nitric acid, the 119 mode (OH torsion relative to the NO2 moiety) is a large amplitude motion. The theoretical model used in this work accounts also for large amplitude effects in the 93 dark state, which lead to a splitting of the 93 energy levels of about 0.060 cm(-1). In this way, the existence of torsional splittings for several v, perturbed lines was explained by the occurrence of local A-type and B-type Coriolis resonances coupling the 41 energy levels with those of 9(3) Because four dark bands had to be accounted for in the model, the results of the energy level calculations are reasonable, although not perfect. However, a very significant improvement was achieved in terms of understanding the 7.6 pm absorbing bands of nitric acid as compared to the analysis of the 113 and 114 bands performed several years ago [Pen-in, A.; Lado-Bordowski, O.; Valentin, A. Mot Phys. 1989, 67, 249-267]. Finally, the present analysis also features, for the first time, the v(3)+v(9)-v(9) hot band located at 1331.09 cm(-1). This study will help to improve HNO3 measurements by satellites. This will be indeed the case for the "Infrared Atmospheric Sounding Interferometer" (/ASI) experiment.