Theoretical calculation of rovibronic energy levels and anharmonic resonances in the ground X 2Π state of HCP+ and DCP+Electronic supplementary information (ESI) available: Expansion coefficients of the PESs (Table). See http://www.rsc.org/suppdata/cp/b1/b107282j/

Abstract

The spin–rovibronic levels of the HCP+ radical cation and its deuteriated isotopomer in the ground X2Π state have been studied using high-level ab initio methods followed by variational calculations on the computed potential energy surfaces. All experimental levels are reproduced within 8 cm−1 and predictions of the rovibronic levels (K≤3) for energies up to 4500 cm−1 for HCP+ and 4000 cm−1 for DCP+ are provided. Anharmonic resonances are analyzed in detail and found to be more complex than previously thought.