Higherorder ldoubling of linear molecules
Abstract
The centrifugal correction q_{t}^{J}J( J + 1) to the ldoubling constant q_{t} corresponds to a term of type H∼_{24} in the effective vibrationrotation Hamiltonian. A general sequential procedure for calculating H∼_{24} is presented, and applied to the particular case of the constant q_{t}^{J} of linear molecules, which depends on the cubic but not the quartic potential constants. Reasonable agreement is obtained with observed values of q_{2}^{J} of CO _{2} and q_{5}^{J} of C _{2}H _{2}. The simple high J behavior of rotational energies with V_{t}>1, when ldoubling dominates the ( g_{tt}  B_{v}) l_{t}^{2} splittings, is discussed.
 Publication:

Journal of Molecular Spectroscopy
 Pub Date:
 September 1983
 DOI:
 10.1016/00222852(83)900085
 Bibcode:
 1983JMoSp.101...83W