High resolution spectroscopy of the OsO4 stretching fundamental at 961 cm−1

Abstract

The ν3 bands of 187Os16O4, 189Os16O4, and 192Os16O4 have been recorded using both a Michelson interferometer (resolution 0.06 cm−1) and a tunable semiconductor diode laser (resolution limited by the Doppler width, ∼0.0007 cm−1). The rotational fine structure differs from that of most other spherical-top molecules, for only rotational levels of A symmetry exist. A total of 112 individual vibration–rotation lines in the P and R branches of the three isotopic species were calibrated against stimulated emission lines from a high-voltage CO2 gain cell, and were used to determine three scalar and two tensor spectroscopic constants for each species; an additional scalar constant was obtained from an analysis of the Q branch of 192OsO4. The strength of P (11) A2 0 was measured for 192OsO4 and yields a vibrational transition moment for ν3 of 0.17±0.02 D. Transitions of all isotopic species that are expected to fall near CO2 laser lines in the region 949–972 cm−1 are tabulated as an aid in the interpreation of saturation spectroscopy experiments. The general quadratic symmetry and valence force constants of OsO4 were redetermined, using the isotope shifts in ν3 as the additional constraints for the F2 symmetry block.