The pure rotational spectrum of the CrS radical in its X Π5r state

Abstract

The pure rotational spectrum of the CrS radical has been measured in its ground X (5)Π(r) state using gas-phase millimeter/submillimeter direct absorption methods. The molecule was created by the reaction of chromium vapor, sublimed in a Broida-type oven, with hydrogen sulfide. Eleven rotational transitions were recorded for this free radical in the frequency range of 280-405 GHz; in most transitions, all five spin components were observed, and lambda-doubling was resolved in the Ω=0, 1, and 2 ladders. The data were fit with a Hund's case (a) Hamiltonian and rotational, spin-orbit, spin-spin, and lambda-doubling constants were established. Higher order spin and spin-orbit terms were essential in the analysis. The lambda-doubling constants indicate a nearby (5)Σ(+) state at an energy of ∼1500-2000 cm(-1). A bond length of 2.0781 Å was derived for CrS from the data, which is larger than the value of 2.0682 Å found for MnS by ∼0.01 Å. In contrast, the bond distance for MnO is greater than that of CrO by 0.03 Å, an illustration of the subtle differences between 3d oxide and sulfides. CrS is the second molecule in a (5)Π state that has been studied by rotational spectroscopy.