Knowledge Bank

We have obtained new high-resolution data on some 25 vibrational levels of the $d^\{3\}\backslash Delta\_\{i\},\; a^\{\backslash prime\}^\{3\}\backslash Sigma^\{+\},\; e^\{3\}\backslash Sigma^\{-\},\; a^\{3\}\backslash Pi$, and $A1\Pi$ states of CS from uv absorption and emission $spectra.1$ Because of numerous perturbation crossings and substantial perturbation shifts from spin-orbit interactions, the extraction of true ""deperturbed"" parameters has presented a challenge to spectral analysis. We have resorted to fittings to Hamiltonian secular equations of dimension as large as $15\times 15$, supplemented by second-order perturbation shifts computed from the empirical electronic state interactions. A sensitive test of the accuracy of the parameters of each state and the derived potential curves is whether the off-diagonal spin-orbit perturbation elements are proportional to the computed vibrational overlap integrals. The results which we present are obtained from several stages of iteration and exhibit consistency in most cases.