Evidence of Vibrational-Induced Rotational Axis Switching for HD(12)C(16)O: New High-Resolution Analysis of the nu(5) and nu(6) Bands and First Analysis of the nu(4) Band (10-µm Region).

Using new high-resolution Fourier transform spectra recorded in Giessen in the 8-12 µm region, a more extended analysis of the nu(5) and nu(6) bands and the first high-resolution study of the nu(4) band of HDCO were performed. As pointed out previously [M. Allegrini, J. W. C. Johns, and A. R. W. McKellar, Can. J. Phys. 56, 859-864 (1978)], the energy levels of the 5(1) and 6(1) states are strongly coupled by A- and B-type Coriolis interactions. On the other hand, it appeared that weaker resonances involving the energy levels of the 4(1) state with those of the 5(1) and 6(1) states also had to be accounted for. Consequently, the calculation of the energy levels was performed taking into account the Coriolis-type resonances linking the energy levels of the {6(1), 5(1), 4(1)} resonating states. Because of the unusually strong Coriolis interaction between nu(5) and nu(6), a nonclassical behavior of the rotational levels of the 5(1) and 6(1) states was observed and it was necessary to use a new Hamiltonian matrix which possesses, as usual, both A- and B-type Coriolis operators in the 5(1) if 6(1) and 6(1) if 4(1) off diagonal blocks but differs from the classical reduced Hamiltonian which is used commonly for planar C(s)-type molecules. More precisely, it proved necessary to include non-orthorhombic terms in the expansion of the rotational Hamiltonian of the 5(1) and 6(1) states. According to the considerations developed by Watson [J. K. G. Watson, in "Vibrational Spectra and Structure," (J. Durig, Ed.), Chap. 1, Elsevier, Amsterdam, 1977], these non-orthorhombic operators which are not symmetry forbidden are usually removed for semirigid C(s)-type molecules by rotational contact transformations. In the present study, the occurrence of terms in {J(x), J(z)} in the expansions of the rotational Hamiltonians for the 5(1) and 6(1) states indicates that the inertial system of HDCO differs for each of the three {6(1), 5(1), 4(1)} resonating states. Therefore, HDCO becomes a good example of vibrational-induced rotational axis switching (VIRAS) which was already suggested as the mechanism responsible for the enhanced densities of coupled states observed in 2-fluoroethanol [H. Li, S. Erza, and L. A. Philips, J. Chem. Phys. 97, 5956-5963 (1992)]. Copyright 2000 Academic Press.