Accurate spectroscopic calculations of the 12 Λ-S states and 27 omega states of NF+ cation including the spin-orbit coupling effect

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

来源：Molecular Physics, 2014, 112(21): 2827-2839.

DOI：10.1080/00268976.2014.914597

• scalar relativistic correction
• potential energy curve
• spin-orbit coupling effect
• spectroscopic parameter
• core-valence correlation correction

This paper studies the potential energy curves (PECs) of 27 Omega states generated from the 12 Lambda-S states (X-2 Pi, 1(2)Sigma(+), 1(2)Sigma(-), 2(2)Sigma(-), A(2)Pi, 1(2)Delta, 1(4)Sigma(+), 1(4)Sigma(-), 2(4)Sigma(-), 1(4)Pi, 2(4)Pi and 1(4)Delta), which are attributed to the first dissociation channel of NF+ cation. Of these 12 states, only 2(2)Sigma(-) and 2(4)Pi are the repulsive ones, which are very different from those reported by G.-S. Kim and D. M. Hirst, Mol. Phys. 86, 1183-1193 (1995). In addition, the 1(2)Delta and 1(4)Sigma(-) states are found to possess the double well. 1(4)Sigma(+), 1(4)Sigma(-) and 1(4)Delta are found to be the inverted states with the spin-orbit coupling effect taken into account, and 1(2)Sigma(+), 1(2)Sigma(-), 1(2)Delta, 1(4)Sigma(+), 2(4)Sigma(-) and 1(4)Delta are found to be the weakly bound states. The PECs are calculated by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with Davidson correction. The convergent behaviour of the present calculations is discussed with respect to the basis set and level of theory. All the PECs are extrapolated to the complete basis set limit. Core-valence correlation and scalar relativistic corrections are included at the same time. The spin-orbit coupling effect is accounted for by the state interaction method with the Breit-Pauli Hamiltonian. The spectroscopic parameters are evaluated and compared with available measurements and other theoretical results. The effect of spin-orbit coupling on the spectroscopic parameters is discussed. The Franck-Condon factors and radiative lifetimes of the transitions from the 1(4)Pi(3/2), 1(4)Sigma(-)(3/2), 1(2)Delta(3/2) and A(2)Sigma(1/2) states to the X-2 Pi(1/2) state are calculated for several low vibrational levels and some necessary discussion is done. It shows that the spectroscopic results reported in this paper can be expected to be reliably predicted ones.

• 出版日期2014-11-2
• 单位河南师范大学