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:
-
- Univ. of Georgia, Athens, GA (United States)
- Publication Date:
- Research Org.:
- Univ. of Georgia, Athens, GA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and 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. https://doi.org/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. https://doi.org/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 = {Wed May 15 00:00:00 EDT 2013},
month = {Wed May 15 00:00:00 EDT 2013}
}
Web of Science
Works referenced in this record:
Electron Spin Resonance Studies of Transient Alkyl Radicals
journal, November 1963
- Fessenden, Richard W.; Schuler, Robert H.
- The Journal of Chemical Physics, Vol. 39, Issue 9
Alkylperoxy and alkyl radicals. 4. Matrix IR spectra and UV photolysis of ethylperoxy and ethyl radicals
journal, June 1987
- Chettur, G.; Snelson, A.
- The Journal of Physical Chemistry, Vol. 91, Issue 13
Fourier transform millimeter-wave spectroscopy of the ethyl radical in the electronic ground state
journal, February 2004
- Kim, Eunsook; Yamamoto, Satoshi
- The Journal of Chemical Physics, Vol. 120, Issue 7
Infrared spectrum of the CH2 out-of-plane fundamental of C2H5
journal, November 1999
- Sears, Trevor J.; Johnson, Philip M.; BeeBe-Wang, Joanne
- The Journal of Chemical Physics, Vol. 111, Issue 20
Vibrational effects on the torsional motion of ethyl radical
journal, November 1999
- Johnson, Philip M.; Sears, Trevor J.
- The Journal of Chemical Physics, Vol. 111, Issue 20
The C 2 H 5 + O 2 Reaction Mechanism: High-Level ab Initio Characterizations
journal, November 2000
- Rienstra-Kiracofe, Jonathan C.; Allen, Wesley D.; Schaefer, Henry F.
- The Journal of Physical Chemistry A, Vol. 104, Issue 44
Rotovibrational spectroscopy of hydrogen peroxide embedded in superfluid helium nanodroplets
journal, January 2011
- Raston, Paul L.; Knapp, Chrissy J.; Jäger, Wolfgang
- Physical Chemistry Chemical Physics, Vol. 13, Issue 42
Rotational and vibrational dynamics of CO[sub 2] and N[sub 2]O in helium nanodroplets
journal, January 2001
- Nauta, K.; Miller, R. E.
- The Journal of Chemical Physics, Vol. 115, Issue 22
Low temperature studies on propionyl benzoyl peroxide and propionyl peroxide. The ethyl radical
journal, April 1976
- Pacansky, J.; Gardini, G. P.; Bargon, Joachim
- Journal of the American Chemical Society, Vol. 98, Issue 9
Addition of Peroxyl Radicals to Alkenes and the Reaction of Oxygen with Alkyl Radicals
journal, May 2000
- Stark, Moray S.
- Journal of the American Chemical Society, Vol. 122, Issue 17
A comparison of the efficiency and accuracy of the quadratic configuration interaction (QCISD), coupled cluster (CCSD), and Brueckner coupled cluster (BCCD) methods
journal, February 1992
- Hampel, Claudia; Peterson, Kirk A.; Werner, Hans-Joachim
- Chemical Physics Letters, Vol. 190, Issue 1-2
Matrix isolation studies of alkyl radicals. The characteristic infrared spectra of primary alkyl radicals
journal, November 1977
- Pacansky, J.; Horne, D. E.; Bargon, J.
- The Journal of Physical Chemistry, Vol. 81, Issue 23
A systematic study of molecular vibrational anharmonicity and vibration—rotation interaction by self-consistent-field higher-derivative methods. Asymmetric top molecules
journal, July 1988
- Clabo, D. Allen; Allen, Wesley D.; Remington, Richard B.
- Chemical Physics, Vol. 123, Issue 2
Helium nanodroplet isolation rovibrational spectroscopy: Methods and recent results
journal, January 2001
- Callegari, Carlo; Lehmann, Kevin K.; Schmied, Roman
- The Journal of Chemical Physics, Vol. 115, Issue 22
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
Rotation in liquid [sup 4]He: Lessons from a highly simplified model
journal, January 2001
- Lehmann, Kevin K.
- The Journal of Chemical Physics, Vol. 114, Issue 10
On the barrier for rotation about the C–C bond of the ethyl radical
journal, May 1980
- Pacansky, J.; Coufal, H.
- The Journal of Chemical Physics, Vol. 72, Issue 9
Infrared Spectroscopy of (HCl) m (H 2 O) n Clusters in Helium Nanodroplets: Definitive Assignments in the HCl Stretch Region
journal, August 2010
- Morrison, Alexander M.; Flynn, Steven D.; Liang, Tao
- The Journal of Physical Chemistry A, Vol. 114, Issue 31
The ethyl radical: Photoionization and theoretical studies
journal, July 1989
- Ruscic, B.; Berkowitz, J.; Curtiss, L. A.
- The Journal of Chemical Physics, Vol. 91, Issue 1
A fifth-order perturbation comparison of electron correlation theories
journal, May 1989
- Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A.
- Chemical Physics Letters, Vol. 157, Issue 6
A theoretical study on the internal rotation and hyperfine structures of the ethyl radical (CH3-CH2)
journal, July 1991
- Suter, H. U.; Ha, Tae-Kyu
- Chemical Physics, Vol. 154, Issue 2
Direct Spectroscopic Observation of Elementary Excitations in Superfluid He Droplets
journal, June 1996
- Hartmann, M.; Mielke, F.; Toennies, J. P.
- Physical Review Letters, Vol. 76, Issue 24
Rotational and vibrational dynamics of ethylene in helium nanodroplets
journal, March 2005
- Lindsay, C. M.; Miller, R. E.
- The Journal of Chemical Physics, Vol. 122, Issue 10
Infrared laser transient absorption spectroscopy of the ethyl radical
journal, January 1996
- Sears, Trevor J.; Johnson, Philip M.; Jin, Pei
- The Journal of Chemical Physics, Vol. 104, Issue 3
Analysis of the structures, infrared spectra, and Raman spectra for methyl, ethyl, isopropyl, and tert-butyl radicals
journal, January 1991
- Pacansky, Jacob; Koch, W.; Miller, M. D.
- Journal of the American Chemical Society, Vol. 113, Issue 1
Infrared spectroscopy of HOOO and DOOO in 4 He nanodroplets
journal, November 2012
- Raston, Paul L.; Liang, Tao; Douberly, Gary E.
- The Journal of Chemical Physics, Vol. 137, Issue 18
Aspects of the Reaction Mechanism of Ethane Combustion. 2. Nature of the Intramolecular Hydrogen Transfer
journal, June 1994
- Quelch, Geoffrey E.; Gallo, Mary M.; Shen, Mingzuo
- Journal of the American Chemical Society, Vol. 116, Issue 11
Mechanism of the C2H5+O2 reaction
journal, July 1997
- Ignatyev, Igor S.; Xie, Yaoming; Allen, Wesley D.
- The Journal of Chemical Physics, Vol. 107, Issue 1
The vibrational and rotational dynamics of acetylene solvated in superfluid helium nanodroplets
journal, November 2001
- Nauta, K.; Miller, R. E.
- The Journal of Chemical Physics, Vol. 115, Issue 18
A chemical interpretation of vibrationally induced barriers to hindered internal rotation
journal, January 1987
- Claxton, Tom A.; Graham, Alison M.
- Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 12
An ab Initio Study of the Transition State and Forward and Reverse Rate Constants for C 2 H 5 ⇌ H + C 2 H 4
journal, January 1996
- Hase, William L.; Schlegel, H. Bernhard; Balbyshev, Vsevolod
- The Journal of Physical Chemistry, Vol. 100, Issue 13
The structure of the ethyl radical
journal, May 1978
- Pacansky, J.; Dupuis, M.
- The Journal of Chemical Physics, Vol. 68, Issue 9
Reaction Energetics for the Abstraction Process C 2 H 3 + H 2 → C 2 H 4 + H
journal, September 2011
- Agarwal, Jay; Turney, Justin M.; Schaefer, Henry F.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 20
Why CCSD(T) works: a different perspective
journal, December 1997
- Stanton, John F.
- Chemical Physics Letters, Vol. 281, Issue 1-3
The symmetry groups of non-rigid molecules
journal, June 1963
- Longuet-Higgins, H. C.
- Molecular Physics, Vol. 6, Issue 5
Photochemical studies on the ethyl radical
journal, January 1979
- Pacansky, J.; Coufal, H.
- The Journal of Chemical Physics, Vol. 71, Issue 7
Calculation of the frequencies and intensities in the infrared spectrum of the ethyl radical
journal, February 1983
- Pacansky, J.; Schrader, B.
- The Journal of Chemical Physics, Vol. 78, Issue 3
Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories
journal, September 1994
- Deegan, Miles J. O.; Knowles, Peter J.
- Chemical Physics Letters, Vol. 227, Issue 3
An ab initio calculation of the rotation and internal-rotation energy levels of the ethyl radical
journal, January 1998
- East, Allan L. L.; Bunker, P. R.
- Chemical Physics Letters, Vol. 282, Issue 1
Assignment of the infrared spectrum for the ethyl radical
journal, January 1982
- Pacansky, J.; Dupuis, M.
- Journal of the American Chemical Society, Vol. 104, Issue 2
Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4 He nanodroplets
journal, May 2013
- Raston, Paul L.; Liang, Tao; Douberly, Gary E.
- The Journal of Chemical Physics, Vol. 138, Issue 17
Fundamental vibrational frequencies and spectroscopic constants for the methylperoxyl radical, CH 3 O 2 , and related isotopologues 13 CH 3 OO, CH 3 18 O 18 O, and CD 3 OO
journal, April 2012
- Agarwal, Jay; Simmonett, Andrew C.; Schaefer, Henry F.
- Molecular Physics, Vol. 110, Issue 19-20
The vibrational energy levels of small transient molecules isolated in neon and argon matrices
journal, December 1994
- Jacox, Marilyn E.
- Chemical Physics, Vol. 189, Issue 2
Anharmonic effects on the structural and vibrational properties of the ethyl radical: A path integral Monte Carlo study
journal, August 2003
- López-Ciudad, Telesforo; Ramı́rez, Rafael; Schulte, Joachim
- The Journal of Chemical Physics, Vol. 119, Issue 8
Aspects of the reaction mechanism of ethane combustion. Conformations of the ethylperoxy radical
journal, October 1992
- Quelch, Geoffrey E.; Gallo, Mary M.; Schaefer, Henry F.
- Journal of the American Chemical Society, Vol. 114, Issue 21
Establishment of the C2H5+O2 reaction mechanism: A combustion archetype
journal, February 2008
- Wilke, Jeremiah J.; Allen, Wesley D.; Schaefer, Henry F.
- The Journal of Chemical Physics, Vol. 128, Issue 7
Calculation of Energy Levels for Internal Torsion and Over‐All Rotation. I. CH 3 BF 2 Type Molecules
journal, January 1955
- Wilson, E. Bright; Lin, Chun Chia; Lide, David R.
- The Journal of Chemical Physics, Vol. 23, Issue 1
Rotationally Resolved Spectroscopy of S in Liquid Helium Clusters: A Molecular Probe of Cluster Temperature
journal, August 1995
- Hartmann, M.; Miller, R. E.; Toennies, J. P.
- Physical Review Letters, Vol. 75, Issue 8
A comparative ab initio study of torsion–inversion coupling in CH3NH2, and
journal, February 2010
- Bhatta, Ram S.; Gao, Amy; Perry, David S.
- Journal of Molecular Structure: THEOCHEM, Vol. 941, Issue 1-3
Vibrationally-induced barriers to hindered rotation
journal, January 1987
- Claxton, Tom A.; Graham, Alison M.
- Journal of the Chemical Society, Chemical Communications, Issue 15
Vibrational Energy Flow in Highly Excited Molecules: Role of Intramolecular Vibrational Redistribution
journal, January 1996
- Nesbitt, David J.; Field, Robert W.
- The Journal of Physical Chemistry, Vol. 100, Issue 31
CH stretch/internal rotor dynamics in ethyl radical: High-resolution spectroscopy in the CH3-stretch manifold
journal, February 2006
- Häber, Thomas; Blair, Andrew C.; Nesbitt, David J.
- The Journal of Chemical Physics, Vol. 124, Issue 5
Infrared Laser Spectroscopy of the CH 3 OO Radical Formed from the Reaction of CH 3 and O 2 within a Helium Nanodroplet
journal, May 2012
- Morrison, Alexander M.; Agarwal, Jay; Schaefer, Henry F.
- The Journal of Physical Chemistry A, Vol. 116, Issue 22
Simple(r) algebraic equation for transition moments of fundamental transitions in vibrational second-order perturbation theory
journal, February 2006
- VÁZquez, Juana; Stanton, John F.
- Molecular Physics, Vol. 104, Issue 3
High-Resolution Spectroscopy of NO in Helium Droplets: A Prototype for Open Shell Molecular Interactions in a Quantum Solvent
journal, November 2005
- von Haeften, K.; Metzelthin, A.; Rudolph, S.
- Physical Review Letters, Vol. 95, Issue 21
Anharmonic molecular force fields: Anharmonic molecular force fields
journal, July 2011
- Császár, Attila G.
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
Variational Transition-State Theory with Optimized Orientation of the Dividing Surface and Semiclassical Tunneling Calculations for Deuterium and Muonium Kinetic Isotope Effects in the Free Radical Association Reaction H + C 2 H 4 → C 2 H 5
journal, July 1999
- Villà, Jordi; Corchado, José C.; González-Lafont, Angels
- The Journal of Physical Chemistry A, Vol. 103, Issue 26
Structures, barriers for internal rotation, vibrational frequencies, and thermodynamic functions of CH 2 FCH 2 , CHF 2 CH 2 , and CF 3 CH 2 radicals: An a b i n i t i o study
journal, November 1990
- Chen, Yonghua; Rauk, Arvi; Tschuikow‐Roux, E.
- The Journal of Chemical Physics, Vol. 93, Issue 9
Superfluid Helium Droplets: A Uniquely Cold Nanomatrix for Molecules and Molecular Complexes
journal, May 2004
- Toennies, J. Peter; Vilesov, Andrey F.
- Angewandte Chemie International Edition, Vol. 43, Issue 20
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients
journal, June 1993
- Watts, John D.; Gauss, Jürgen; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 98, Issue 11
Free radicals in superfluid liquid helium nanodroplets: A pyrolysis source for the production of propargyl radical
journal, July 2002
- Küpper, Jochen; Merritt, Jeremy M.; Miller, Roger E.
- The Journal of Chemical Physics, Vol. 117, Issue 2
Inelastic Scattering of Thermal Neutrons from Liquid Helium
journal, January 1971
- Cowley, R. A.; Woods, A. D. B.
- Canadian Journal of Physics, Vol. 49, Issue 2
Laser spectroscopy of jet-cooled ethyl radical: Infrared studies in the CH2 stretch manifold
journal, January 2000
- Davis, Scott; Uy, Dairene; Nesbitt, David J.
- The Journal of Chemical Physics, Vol. 112, Issue 4
Infrared spectroscopy of helium nanodroplets: novel methods for physics and chemistry
journal, January 2006
- Choi, M. Y.; Douberly, G. E.; Falconer, T. M.
- International Reviews in Physical Chemistry, Vol. 25, Issue 1-2
The equilibrium structure and fundamental vibrational frequencies of dioxirane
journal, May 1998
- Stanton, John F.; Lopreore, Courtney L.; Gauss, Jürgen
- The Journal of Chemical Physics, Vol. 108, Issue 17
Automation of an “Aculight” continuous-wave optical parametric oscillator
journal, January 2013
- Morrison, Alexander M.; Liang, Tao; Douberly, Gary E.
- Review of Scientific Instruments, Vol. 84, Issue 1
Works referencing / citing this record:
Quantum-classical dynamics of the capture of neon atoms by superfluid helium nanodroplets
journal, January 2018
- Blancafort-Jorquera, Miquel; Vilà, Arnau; González, Miguel
- Physical Chemistry Chemical Physics, Vol. 20, Issue 47
tert -Butyl peroxy radical: ground and first excited state energetics and fundamental frequencies
journal, January 2019
- Franke, Peter R.; Moore, Kevin B.; Schaefer, Henry F.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 19
An integrated experimental and quantum-chemical investigation on the vibrational spectra of chlorofluoromethane
journal, October 2013
- Charmet, Andrea Pietropolli; Stoppa, Paolo; Tasinato, Nicola
- The Journal of Chemical Physics, Vol. 139, Issue 16
Infrared spectroscopy in superfluid helium droplets
journal, December 2018
- Verma, Deepak; Tanyag, Rico Mayro P.; O’Connell, Sean M. O.
- Advances in Physics: X, Vol. 4, Issue 1