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

Title: 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 ^[1]; Turney, Justin M. ^[1]; Schaefer, III, Henry F. ^[1];

^[1]

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.

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

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

Grant/Contract Number:: SC0008086

OSTI ID:: 1409046

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

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

Country of Publication:: United States

Language:: English

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Cited by: 25 works

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