Magneto-infrared spectra of the Si2, Ge2, and Sn2 molecules in rare-gas matrices

Abstract

Absorption spectra of Si2, Ge2, and Sn2, observed between 50 and 5000 cm−1 in neon and argon matrices at 4 K, were assigned to the lowest 3Πu←X 3Σg− electronic transition. In all three cases, the Franck–Condon envelope of vibrational bands allowed T00, ωe′, ωe′xe′ to be determined. In the Si2 molecule [near Case (a)] T00=313 cm−1 and each vibrational band was split into Ω triplets (0,1,2) in the upper state. A Zeeman effect on these lines was detected in magnetic fields up to 4 T. As the spin–orbit coupling becomes larger in Ge2 and Sn2, the 1u←X0+g transition [case (c)] was observed, and the corresponding parameters in the upper state determined. For Sn2 the magnetic-dipole 1g←X0+g transition was also detected and identified by the splitting and broadening of the band in magnetic fields up to 4 T. The results are discussed in the context of the ab initio calculations and other experimental results on these molecules.