Fourfold Clusters of Rovibrational Energy Levels in the Fundamental Vibrational States of H2Se

Abstract

We report here a calculation of the rotation-vibration energies in the ν1, ν2, ν3, and 2ν2 vibrational states of H280Se using the MORBID (Morse oscillator rigid bender internal dynamics) Hamiltonian and computer program [P. Jensen, J. Mol. Spectrosc.128, 478-501 (1988); J. Chem. Soc. Faraday Trans. 284, 1315-1340 (1988)]. As input data for the calculation, we employ a potential energy surface recently determined from experimental data by means of the MORBID approach [P. Jensen and I. N. Kozin. J. Mol. Spectrosc., in press.]. For all of the vibrational states considered. the calculation shows that as J increases, fourfold rovibrational energy clusters are formed. This effect has already been experimentally verified for the vibrational ground state and its origin was shown to lie in the centrifugal distortion of the molecule [I. N. Kozin, S. P. Belov, O. L. Polyansky, and M. Yu. Tretyakov, J. Mol. Spectrosc.152, 13-28 (1992); I. N. Kozin, O. L. Polyansky, S. I. Pripolzin, and V. L. Vaks, J. Mol. Spectrosc.156, 504-506 ( l992); I. N. Kozin, S. Klee, P. Jensen, O. L. Polyansky, and I. M. Pavlichenkov, J. Mol. Spectrosc.,158, 409-422 (1993)]. We find here that the cluster formation in the ν2 and 2ν2 vibrational states is completely analogous to that in the vibrational ground state. For the ν1/ν3 interacting vibrational states, however, we predict a new type of fourfold clusters. We can describe their formation as a coalescence (with increasing J) of two energy doublets, where one doublet belongs to the ν1 vibrational state and the other one to the ν3 vibrational state, An interpretation of the "new" cluster eigenstates is given, and the origins of the cluster formation are discussed in terms of semiclassical theory. The semiclassical analysis shows that the new clusters are caused essentially bx the rotational interactions between the ν1 and the ν3 states. The predicted term values from the present work are found to be in good agreement with experimental values from a very recent study by J.-M. Flaud, C. Camy-Peyret, H. Bürger, and H. Willner, J. Mol. Spectrosc.161, 157-169 (1993). However, the available experimental data do not extend to sufficiently high J and K values to allow an experimental verification of the existence of the new clusters.