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 [S. Davis, D. Uy, and D. J. Nesbitt, J. Chem. Phys. 112, 1823 (2000) https://doi.org/10.1063/1.480746; T. Häber, A. C. Blair, D. J. Nesbitt, and M. D. Schuder, J. Chem. Phys. 124, 054316 (2006) https://doi.org/10.1063/1.2140740]. 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. 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.
Skip Nav Destination
,
,
,
,
Article navigation
21 May 2013
Research Article|
May 15 2013
The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations Available to Purchase
Paul L. Raston;
Paul L. Raston
1Department of Chemistry,
University of Georgia
, Athens, Georgia 30602-2556, USA
Search for other works by this author on:
Jay Agarwal;
Jay Agarwal
2Center for Computational Chemistry,
University of Georgia
, Athens, Georgia 30602-2556, USA
Search for other works by this author on:
Justin M. Turney;
Justin M. Turney
2Center for Computational Chemistry,
University of Georgia
, Athens, Georgia 30602-2556, USA
Search for other works by this author on:
Henry F. Schaefer, III;
Henry F. Schaefer, III
2Center for Computational Chemistry,
University of Georgia
, Athens, Georgia 30602-2556, USA
Search for other works by this author on:
Gary E. Douberly
Gary E. Douberly
a)
1Department of Chemistry,
University of Georgia
, Athens, Georgia 30602-2556, USA
Search for other works by this author on:
Paul L. Raston
1
Jay Agarwal
2
Justin M. Turney
2
Henry F. Schaefer, III
2
Gary E. Douberly
1,a)
1Department of Chemistry,
University of Georgia
, Athens, Georgia 30602-2556, USA
2Center for Computational Chemistry,
University of Georgia
, Athens, Georgia 30602-2556, USA
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]. Tel.: 01-706-542-3857.
J. Chem. Phys. 138, 194303 (2013)
Article history
Received:
March 08 2013
Accepted:
April 23 2013
Citation
Paul L. Raston, Jay Agarwal, Justin M. Turney, Henry F. Schaefer, Gary E. Douberly; The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations. J. Chem. Phys. 21 May 2013; 138 (19): 194303. https://doi.org/10.1063/1.4804435
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
The Amsterdam Modeling Suite
Evert Jan Baerends, Nestor F. Aguirre, et al.
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets
J. Chem. Phys. (May 2013)
Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene
J. Chem. Phys. (April 2015)
Near-resonant rotational energy transfer in HCl–H2 inelastic collisions
J. Chem. Phys. (February 2014)
Interchange-tunneling splitting in HCl dimer in helium nanodroplets
J. Chem. Phys. (March 2008)
Infrared spectroscopy of HCN-salt complexes formed in liquid-helium nanodroplets
J. Chem. Phys. (February 2006)