Theoretical study on HBO+ and HOB+ cations using multiconfiguration second‐order perturbation theory

The HBO+ and HOB+ cations have been reinvestigated using the CASSCF and CASPT2 methods in conjunction with the contracted atomic natural orbital (ANO) basis sets. The geometries of all stationary points in the potential energy surfaces were optimized at the CASSCF/ANO and CASPT2/ANO levels. The ground and the first excited states of HBO+ are predicted to be X2Π and A2Σ+ states, respectively. It was predicted that the ground state of HOB+ is X2Σ+ state. The A2Π state of HOB+ has unique imaginary frequency. A bending local minimum M1 was found for the first time along the 12A′′ potential energy surface and the A2Π state of HOB+ should be the transition state of the isomerization reactions for M1↔ M1. The CASPT2/ANO potential energy curves (PECs) of isomerization reactions were calculated as functions of the HBO bond angle. Many of the CASSCF and CASPT2 calculated results were different from the previously published QCISD(T) results. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010