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Precise spectroscopic analysis of polyatomic molecules enables many strikingadvances in physical chemistry and fundamental physics. We use several newhigh-resolution spectroscopic devices to improve our understanding of therotational and rovibrational structure of methyltrioxorhenium (MTO), theachiral parent of a family of large oxorhenium compounds that are idealcandidate species for a planned measurement of parity violation in chiralmolecules. Using millimetre-wave and infrared spectroscopy in a pulsedsupersonic jet, a cryogenic buffer gas cell, and room temperature absorptioncells, we probe the ground state and the Re=O antisymmetric and symmetricstretching excited states of both CH3 187 ReO3 and CH3 185 ReO3 isotopologuesin the gas phase with unprecedented precision. By extending the rotationalspectra to the 150-300 GHz range, we characterize the ground state rotationaland hyperfine structure up to J = 43 and K = 41, resulting in refinements tothe rotational, quartic and hyperfine parameters, and the determination ofsextic parameters and a centrifugal distortion correction to the quadrupolarhyperfine constant. We obtain rovibrational data for temperatures between 6 and300 K in the 970-1015 cm-1 range, at resolutions down to 8 MHz and accuraciesof 30 MHz. We use these data to determine more precise excited-staterotational, Coriolis and quartic parameters, as well as the ground-statecentrifugal distortion parameter D K of the 187 Re isotopologue. We alsoaccount for hyperfine structure in the rovibrational transitions and hencedetermine the upper state rhenium atom quadrupole coupling constant eQq' .

physical chemistry chemical physics/pccp. physical chemistry chemical physics

Characterising molecules for fundamental physics: an accurate  spectroscopic model of methyltrioxorhenium derived from new infrared and  millimetre-wave measurements