The lower excited states of CS: A study of extensive spin-orbit perturbations

Abstract

We present previously unpublished data on the A1Π, e3Σ−, d3Δi, a′ 3Σ+, and a3Π states of CS from uv emission and absorption transitions to the X1Σ+ ground state. Term values obtained from d3Δi ← a3Π ir emission bands are also included. Rotational analyses are presented for about 50 new fine-structure components in some 30 new vibrational levels, together with extended data and analyses for many of the previously observed levels. The data now availabe for these five electronic states more than triples that previously published. Vibrational numbering for the e, d, and a′ states is established by data for minor isotopes. In a Hund's case a-b basis, off-diagonal spin-orbit elements (incipient case c effects) produce extensive coupling among these levels, not only for perturbation crossings but also between levels widely separated in energy. A systematic deperturbation requires two stages, which are iterated. Term values computed from the spectral lines are used to fit parameters of Hamiltonian matrices for groups of nearby, coupled levels. Additional shifts are computed by second-order perturbation theory from the electronic interactions deduced from vibronic coupling elements. The resultant parameters satisfy certain tests for self-consistency; they conform to low-order polynomials in v + 12, and vibrational overlap factors from wave-functions computed with RKR potential curves are proportional to the vibronic coupling elements, to within experimental error in most cases. To obtain this self-consistency, we have computed and applied normally neglected centrifugal distortion effects in the off-diagonal coupling elements and in the second-order perturbation sums. We also present and interpret the diagonal spin-orbit fine structure in the a and d states, including the centrifugal distortion parameters, AD, for the latter, and values for several fitted second-order elements. Possible assignments for three additional perturbations of the A1Π state and one faint band are discussed in view of 1Δ, 1Σ−, and 5Π states that are also expected to occur in the region studied. Tentative parameters for the D1Δ state are obtained from one possible set of assignments.