A vacuum-ultraviolet laser pulsed field ionization-photoelectron study of sulfur monoxide (SO) and its cation (SO+)

Vacuum ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) spectroscopy has been applied to the study of the sulfur monoxide radical (SO) prepared by using a supersonically cooled radical beam source based on the 193 nm excimer laser photodissociation of SO2. The vibronic VUV-PFI-PE bands for the photoionization transitions SO+(X-2 Pi(1/2); v(+) = 0) <- SO(X-3 Sigma(-); v = 0); and SO+((2)Pi(3/2); v(+) = 0) <- SO(X-3 Sigma(-); v = 0) have been recorded. On the basis of the semiempirical simulation of rotational branch contours observed in these PFI-PE bands, we have obtained highly precise ionization energies (IEs) of 83 034.2 +/- 1.7 cm(-1) (10.2949 +/- 0.0002 eV) and 83 400.4 +/- 1.7 cm(-1) (10.3403 +/- 0.0002 eV) for the formation of SO+(X-2 Pi(1/2); v(+) = 0) and SO+((2)Pi(3/2); v(+) = 0), respectively. The present VUV-PFI-PE measurement has enabled the direct determination of the spin-orbit coupling constant (A(0)) for SO+(X-2 Pi(1/2,3/2)) to be 365.36 +/- 0.12 cm(-1). We have also performed high-level ab initio quantum chemical calculations at the coupled-cluster level up to full quadruple excitations and complete basis set (CBS) extrapolation. The zero-point vibrational energy correction, the core-valence electronic correction, the spin-orbit coupling, and the high-level correction are included in the calculation. The IE[SO+(X-2 Pi(1/2,3/2))] and A(0) predictions thus obtained are found to be in remarkable agreement with the experimental determinations. (C) 2011 American Institute of Physics. [doi:10.1063/1.3575227]