Photodissociation spectra of transition metal sulfides: spin-orbit structure in charge transfer bands of FeS+ and NiS+

Photofragment spectra of FeS+ and NiS+ are reported. Analysis of the FeS+ s pectrum reveals it to arise from a 6 Pi <-- (6)Sigma charge-transfer transi tion, and gives the vibrational frequency, omega (e)' = 295 cm(-1), and spi n-orbit constant, \A \ = 125 cm(-1), in the hn state. The onset of the NiS spectrum appears to occur in the middle of a vibrational progression, thus giving a precise measurement of the Ni+-S bond strength, D-0(Ni+-S) = 238 +/- 4 kJ mol(-1). Analysis of the spectrum for vibrational and spin-orbit s tructure leads to a tentative assignment of a (4)Delta ground state and sug gests the spectrum is composed of overlapping transitions to two near-degen erate excited electronic states, most likely a (4)Pi and (4)Phi, pair. (C) 2001 Elsevier Science B.V. All rights reserved.