Abstract
The potential energy curves (PECs) of the X2Π and A2Π electronic states of the SO+ ion are calculated using the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction (MRCI) approach for internuclear separations from 0.08 to 1.06 nm. The spin-orbit coupling effect on the spectroscopic parameters is included using the Breit-Pauli operator. To improve the quality of PECs and spin-orbit coupling constant (A0), core-valence correlation and scalar relativistic corrections are included. To obtain more reliable results, the PECs obtained by the MRCI calculations are corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). At the MRCI+Q/aug-cc-pV5Z+CV+DK level, the A0 values of the SO+(X2Π1/2, 3/2) and SO+(A2Π1/2, 3/2) are 362.13 and 58.16 cm−1 when the aug-cc-pCVTZ basis set is used to calculate the spin-orbit coupling splitting, and the A0 of the SO+(X2Π1/2, 3/2) and SO+(A2Π1/2, 3/2) are 344.36 and 52.90 cm−1 when the aug-cc-pVTZ basis set is used to calculate the spin-orbit coupling splitting. The conclusion is drawn that the core-valence correlations correction makes the A0 slightly larger. The spectroscopic results are obtained and compared with those reported in the literature. Excellent agreement exists between the present results and the measurements. The vibrational manifolds are calculated, and those of the first 30 vibrational states are reported for the J = 0 case. Comparison with the measurements shows that the present vibrational manifolds are both reliable and accurate.
Highlights
The SO+ ion is an important species of considerable physical, chemical and astrophysical interest.The ion is isovalent to O2+ and is one of the main constituents of plasmas containing sulfur and oxygen
The shift of the Te lowered by the modification is 756.53 cm−1; (2) the Davidson modification lengthens the Re only by 0.00019 and 0.00013 nm for the X2Π and A2Π electronic states, respectively; (3) the effects on the ωe by the Davidson modification are unequal for the two electronic states
SO+(A2Π1/2, 3/2) obtained by the ACVTZ basis set agree well with the measurements [17], and the difference between such A0 result and the experimental one is only several cm−1; (2) the core-valence correlations make the A0 become large for the two electronic states but are not sure to increase the accuracy of the spin-orbit coupling constant A0; (3) the spectroscopic results determined by the multireference configuration interaction (MRCI)+Q/AV5Z+CV+DK calculations for the X2Π and A2Π electronic states have achieved a high quality
Summary
The SO+ ion is an important species of considerable physical, chemical and astrophysical interest. In the past more than thirty years, a number of experiments [10,11,12,13,14,15,17,18,20,22] have been made to determine the spin-orbit coupling constant (A0) of the SO+(X2Π1/2, 3/2) and SO+(A2Π1/2, 3/2) Of these experiments, the first one was made by Dyke et al [10] in 1974, who measured the experimental A0 value, 340 ± 10 cm−1 for the SO+(X2Π1/2, 3/2) using photoelectron spectrometer. 359.0 cm−1 for the SO+(X2Π1/2, 3/2) was obtained in their calculations As we know, both the core-valence correlation and scalar relativistic corrections have important effects on the accurate prediction of the spectroscopic parameters and molecular constants. Using the Breit-Pauli operator, the spin-orbit coupling effect on the spectroscopic parameters is included in the present PEC calculations of the X2Π and A2Π electronic states by two basis sets, aug-cc-pCVTZ (ACVTZ) and aug-cc-pVTZ (AVTZ) [33,34]. Comparison with the measurements demonstrates that the present results are much more accurate and reliable than the ones obtained by previous theoretical calculations
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