Accurate multireference configuration interaction calculations of the 24 Λ-S states and 60 Ω states of the BO(+) cation.
The potential energy curves were calculated for the 24 Λ-S states correlating with the lowest four dissociation channels of the BO(+) cation. The potential energy curves were also computed for the 60 Ω states generated from the 24 Λ-S states. Calculations were made for internuclear separations from 0.08 to 1.05nm using the CASSCF method, which was followed by the icMRCI approach with the correlation-consistent basis sets. Core-valence correlation, scalar relativistic and basis extrapolation were accounted for. Of the 24 Λ-S states, only three states (2(5)Π, 1(5)Σ(-), and 2(5)Σ(-)) were found to be repulsive; only the 1(5)Δ state was found to be a very weakly-bound state; and the E(1)Π, 2(3)Π, and 1(5)Π states were found to be very strong bound. In addition, the B(1)Σ(+) and 3(1)Σ(+) states have double wells by the avoided crossing between the two states. The a(3)Π, 1(3)Σ(-), and 2(3)Σ(-) states are inverted with the spin-orbit coupling effect included. The spectroscopic parameters were determined and the vibrational properties of several Λ-S states were predicted. Comparison with available experimental data shows that the methodology employed is highly accurate for this system.
College of Physics and Electronic Engineering, Henan Normal University, Xinxiang 453007, China; College of Physics and Electronic Engineering, Xinyang Normal University, Xinyang 464000, China.
Hui
H
Liu
College of Physics and Electronic Engineering, Henan Normal University, Xinxiang 453007, China. Electronic address: scattering@sina.com.cn.
Deheng
D
Shi
College of Physics and Electronic Engineering, Henan Normal University, Xinxiang 453007, China.
Jinfeng
J
Sun
College of Physics and Electronic Engineering, Henan Normal University, Xinxiang 453007, China.
Zunlue
Z
Zhu
Core–valence correlation correction; Potential energy curve; Scalar relativistic correction; Spectroscopic parameter; Spin–orbit coupling