The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations

Raston, Paul L.; Agarwal, Jay; Turney, Justin M.; Schaefer, III, Henry F.; Douberly, Gary E.

doi:10.1063/1.4804435

The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations

Journal Article · Wed May 15 00:00:00 EDT 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4804435· OSTI ID:1409046

Raston, Paul L. ^[1]; Agarwal, Jay ^[2]; Turney, Justin M. ^[2]; Schaefer, III, Henry F. ^[2]; ^[2]

Univ. of Georgia, Athens, GA (United States); University of Georgia, Athens, GA
Univ. of Georgia, Athens, GA (United States)

The ethyl radical has been isolated and spectroscopically characterized in 4He nanodroplets. The band origins of the five CH stretch fundamentals are shifted by < 2 cm^–1 from those reported for the gas phase species. The symmetric CH₂ stretching band (v₁) is rotationally resolved, revealing nuclear spin statistical weights predicted by G₁₂ permutation-inversion group theory. A permanent electric dipole moment of 0.28 (2) D is obtained via the Stark spectrum of the v₁ band. The four other CH stretch fundamental bands are significantly broadened in He droplets and lack rotational fine structure. This broadening is attributed to symmetry dependent vibration-to-vibration relaxation facilitated by the He droplet environment. In addition to the five fundamentals, three a₁' overtone/combination bands are observed, and each of these have resolved rotational substructure. As a result, these are assigned to the 2v₁₂, v₄ + v₆, and 2v₆ bands through comparisons to anharmonic frequency computations at the CCSD(T)/cc-pVTZ level of theory.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Georgia Research Foundation, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008086

OSTI ID:: 1409046

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 138; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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