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

Abstract

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.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Research Org.:
Univ. of Georgia Research Foundation, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1409046
Grant/Contract Number:  
SC0008086
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 138; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Raston, Paul L., Agarwal, Jay, Turney, Justin M., Schaefer, III, Henry F., and Douberly, Gary E. The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations. United States: N. p., 2013. Web. doi:10.1063/1.4804435.
Raston, Paul L., Agarwal, Jay, Turney, Justin M., Schaefer, III, Henry F., & Douberly, Gary E. The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations. United States. doi:10.1063/1.4804435.
Raston, Paul L., Agarwal, Jay, Turney, Justin M., Schaefer, III, Henry F., and Douberly, Gary E. Wed . "The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations". United States. doi:10.1063/1.4804435. https://www.osti.gov/servlets/purl/1409046.
@article{osti_1409046,
title = {The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations},
author = {Raston, Paul L. and Agarwal, Jay and Turney, Justin M. and Schaefer, III, Henry F. and Douberly, Gary E.},
abstractNote = {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.},
doi = {10.1063/1.4804435},
journal = {Journal of Chemical Physics},
number = 19,
volume = 138,
place = {United States},
year = {2013},
month = {5}
}

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