Kramers-Type Splitting in the X2Π and a4Σ− States of CH and CD Calculated in a Hund's Case (a) Basis
✍ Scribed by Martin Kleinschmidt; Timo Fleig; Christel M. Marian
- Publisher
- Elsevier Science
- Year
- 2002
- Tongue
- English
- Weight
- 192 KB
- Volume
- 211
- Category
- Article
- ISSN
- 0022-2852
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✦ Synopsis
We present relativistic ab initio calculations of spectroscopic parameters and rotational term energies of the CH and CD molecules. Potential energy curves have been obtained for a scalar relativistic no-pair Hamiltonian using a multireference configuration interaction (MRCI) approach. Rovibronic couplings have been computed for the ground and first excited states X 2 and a 4 -. These have been determined through perturbation theory based upon vibronic CI wavefunctions. All important angular momentum couplings including spin-orbit interaction are accounted for, which leads to a correct description of intermediate states between Hund's cases (a) and (b). Experimental values are reproduced very well, and we give some predictions for excited states.