Accurate spectroscopic calculations of the 14 Lambda-S and 30 Omega states of BF+ cation including the spin-orbit coupling effect

作者：Zhu, Wenjie; Shi, Deheng^*; Sun, Jinfeng; Zhu, Zunlue

来源：Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy , 2017, 171: 478-486.

DOI：10.1016/j.saa.2016.08.020

• BF+ cation, spectroscopic parameter
• Scalar relativistic correction
• Potential energy curve
• Spin-orbit coupling effect
• Core-valence correlation correction

This paper studied the potential energy curves of 30 Omega states yielded from the 14 Lambda-S states (X-2 Sigma(+), 1(2)Pi, 2(2)Pi, 3(2)Pi, 1(2)Sigma(-), 2(2)Sigma(+), 3(2)Sigma(+),1(2)Delta, 1(4)Sigma(-), 1(4)Sigma(+), 2(4)Sigma(+), 1(4)Pi, 2(4)Pi, and 1(4)Delta) of the BF+ cation. The potential energy curves were calculated for internuclear separations from approximately 0.08 to 1.1 nm using the CASSCF method, which was followed by the icMRCI approach with the aug-cc-pV6Z basis set. Of these 14 Lambda-S states, the 2(4)Sigma(+) and 2(4)Pi states were repulsive. The 2(2)Pi and 3(2)Pi states had double wells. The avoided crossings were found between the 1(2)Pi and the 2(2)Pi state, and between the 3(2)Pi and the 4(2)Pi state. The 1(2)Pi, 2(2)Pi, 3(2)Pi and 1(4)Pi states were inverted with the spin-orbit coupling effect taken into account. The 1(4)Pi state and the second wells of 2(2)Pi and 3(2)Pi states were weakly bound. Each of the 1(2)Pi, 2(2)Pi, and 3(2)Pi states had one barrier. The potential energy curves of all the Lambda-S and Omega states were extrapolated to the complete basis set limit. Core-valence correlation and scalar relativistic corrections were included at the level of an aug-cc-pV5Z basis set. The spin-orbit coupling effect was included by the state interaction approach with the Breit-Pauli Hamiltonian and the all-electron cc-pCV5Z set. The spectroscopic parameters were determined and compared with available experimental and other theoretical ones. The spin-orbit coupling effect on the spectroscopic parameters was evaluated in detail. Comparison with available experimental data show that the methodology used in this paper is highly accurate for this system.

• 出版日期2017-1-15
• 单位河南师范大学