Symmetry-adapted-cluster configuration interaction study of the doublet states of HCl+: Potential energy curves, dipole moments, and transition dipole moments

摘要

The electronic structure of the HCl+ molecular ion has been calculated using the general-R symmetry-adapted-cluster configuration interaction (SAC-CI) method. The authors present the potential energy curves, dipole moments, and transition dipole moments for a series of doublet states. The data are compared with the previous CASSCF and MCSCF calculations. The SAC-CI results reproduce quite well the data available in literature and extend the knowledge on the HCl+ electronic structure for several higher states. The calculated R-dependent behavior of both dipole moments and transition dipole moments for a series of bound and unbound states reveals an intricate dissociation process at intermediate distances (R > R-e). The pronounced maxima in transition dipole moment (TDM) describing transitions into high electronic states (X (2)Pi -> 3 (2)Pi, X (2)Pi -> 3 (2)Sigma, 2 (2)Pi -> 3 (2)Pi, 3 (2)Pi -> 4 (2)Pi) occur at different interatomic separations. Such TDM features are promising for selection of excitation pathways and, consequently, for an optimal control of the dissociation products. (c) 2007 American Institute of Physics.