Millimeter-wave optical double resonance schemes for rapid assignment of perturbed spectra, with applications to the [~ over C] [superscript 1]B[subscript 2] state of SO[subscript 2]
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Author(s)
Womack, Caroline C.
Jiang, Jun
Ono, Shuhei
Whitehill, Andrew Richard
Field, Robert W
Park III, George Barratt
Date Issued
April 2015
Journal
The Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
Park, G. Barratt, Caroline C. Womack, Andrew R. Whitehill, Jun Jiang, Shuhei Ono, and Robert W. Field. “Millimeter-Wave Optical Double Resonance Schemes for Rapid Assignment of Perturbed Spectra, with Applications to the [~ over C] [superscript 1]B[subscript 2] State of SO[subscript 2].” The Journal of Chemical Physics 142, no. 14 (April 14, 2015): 144201. © 2015 AIP Publishing LLC
Version
Final published version
Abstract
Millimeter-wave detected, millimeter-wave optical double resonance (mmODR) spectroscopy is a powerful tool for the analysis of dense, complicated regions in the optical spectra of small molecules. The availability of cavity-free microwave and millimeter wave spectrometers with frequency-agile generation and detection of radiation (required for chirped-pulse Fourier-transform spectroscopy) opens up new schemes for double resonance experiments. We demonstrate a multiplexed population labeling scheme for rapid acquisition of double resonance spectra, probing multiple rotational transitions simultaneously. We also demonstrate a millimeter-wave implementation of the coherence-converted population transfer scheme for background-free mmODR, which provides a ∼10-fold sensitivity improvement over the population labeling scheme. We analyze perturbations in the [~ over C] state of SO[subscript 2], and we rotationally assign a b[subscript 2] vibrational level at 45 328 cm[superscript −1] that borrows intensity via a c-axis Coriolis interaction. We also demonstrate the effectiveness of our multiplexed mmODR scheme for rapid acquisition and assignment of three predissociated vibrational levels of the [~ over C] state of SO[subscript 2] between 46 800 and 47 650 cm[superscript −1].
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences
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DOI of Published Version
https://doi.org/10.1063/1.4916908
