THE ETHYL RADICAL IN SUPERFLUID HELIUM NANODROPLETS: ROVIBRATIONAL SPECTROSCOPY AND AB INITIO CALCLUATIONS

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The ethyl radical has been isolated and spectroscopically characterized in 4He nanodroplets. The five fundamental CH stretch bands are observed near 3 μm and have band origins shifted Misplaced &<< 1 \wn from those reported for the gas phase species. \textbf{112}, 1823-1834 (2000).}, \textbf{124}, 054316 (2006).} The symmetric CH2 stretching band (\textit{ν1}) is rotationally resolved, revealing nuclear spin statistical weights predicted by \textit{G12} permutation-inversion group theory. A permanent electric dipole moment of 0.28 (2) D is obtained via the Stark spectrum of the \textit{ν1} band. The four other CH stretch fundamental bands are broadened in helium droplets and lack rotational fine structure. The approximately 1-2 \wn line widths for these bands are attributed to the homogeneous broadening associated with solvent-mediated rovibrational relaxation dynamics. In addition to these five fundamentals, three \textit{A1} overtone/combination bands are observed and have resolved rotational substructure. These are assigned to the 2\textit{ν12}, \textit{ν4}+\textit{ν6}, and 2\textit{ν6} bands through comparisons to anharmonic frequency computations at the CCSD(T)/cc-pVTZ level of theory.

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Author Institution: Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556; Center for Computational Chemistry, University of Georgia, Athens, Georgia 30602-2556; Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556

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