Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals

Leavitt, Christopher M.; Moradi, Christopher P.; Acrey, Bradley W.; Douberly, Gary E.

doi:10.1063/1.4844175

Title: Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals

Abstract

Infrared spectra in the C–H stretch region are reported for the allyl (CH₂CHCH₂) and allyl peroxy (CH₂=CH–CH₂OO·) radicals solvated in superfluid helium nanodroplets. Nine bands in the spectrum of the allyl radical have resolved rotational substructure. We have assigned three of these to the ν₁ (a₁), ν₃ (a₁), and ν₁₃ (b₂) C–H stretch bands and four others to the ν₁₄/(ν₁₅+2ν₁₁) (b₂) and ν₂/(ν₄+2ν₁₁) (a₁) Fermi dyads, and an unassigned resonant polyad is observed in the vicinity of the ν₁ band. Experimental coupling constants associated with Fermi dyads are consistent with quartic force constants obtained from density functional theory computations. The peroxy radical was formed within the He droplet via the reaction between allyl and O₂ following the sequential pick-up of the reactants. Five stable conformers are predicted for the allyl peroxy radical, and a computed two-dimensional potential surface for rotation about the CC–OO and CC–CO bonds reveals multiple isomerization barriers greater than ≈300 cm^–1. Furthermore, the C–H stretch infrared spectrum is consistent with the presence of a single conformer following the allyl + O₂ reaction within helium droplets.

Authors:

Leavitt, Christopher M. ^[1]; Moradi, Christopher P. ^[1]; Acrey, Bradley W. ^[1];

^[1]

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

Publication Date:: Mon Dec 16 00:00:00 EST 2013

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:: 1409050

Grant/Contract Number:: SC0008086

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 139; Journal Issue: 23; 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


                    Leavitt, Christopher M., Moradi, Christopher P., Acrey, Bradley W., and Douberly, Gary E. Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals.  United States: N. p., 2013. 
        Web.  doi:10.1063/1.4844175.

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                    Leavitt, Christopher M., Moradi, Christopher P., Acrey, Bradley W., & Douberly, Gary E. Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals.  United States.  https://doi.org/10.1063/1.4844175

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                    Leavitt, Christopher M., Moradi, Christopher P., Acrey, Bradley W., and Douberly, Gary E. 2013.  
        "Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals".  United States.  https://doi.org/10.1063/1.4844175.  https://www.osti.gov/servlets/purl/1409050.

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@article{osti_1409050,

  title        = {Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals},

  author       = {Leavitt, Christopher M. and Moradi, Christopher P. and Acrey, Bradley W. and Douberly, Gary E.},

  abstractNote = {Infrared spectra in the C–H stretch region are reported for the allyl (CH2CHCH2) and allyl peroxy (CH2=CH–CH2OO·) radicals solvated in superfluid helium nanodroplets. Nine bands in the spectrum of the allyl radical have resolved rotational substructure. We have assigned three of these to the ν1 (a1), ν3 (a1), and ν13 (b2) C–H stretch bands and four others to the ν14/(ν15+2ν11) (b2) and ν2/(ν4+2ν11) (a1) Fermi dyads, and an unassigned resonant polyad is observed in the vicinity of the ν1 band. Experimental coupling constants associated with Fermi dyads are consistent with quartic force constants obtained from density functional theory computations. The peroxy radical was formed within the He droplet via the reaction between allyl and O2 following the sequential pick-up of the reactants. Five stable conformers are predicted for the allyl peroxy radical, and a computed two-dimensional potential surface for rotation about the CC–OO and CC–CO bonds reveals multiple isomerization barriers greater than ≈300 cm–1. Furthermore, the C–H stretch infrared spectrum is consistent with the presence of a single conformer following the allyl + O2 reaction within helium droplets.},

  doi          = {10.1063/1.4844175},

  url          = {https://www.osti.gov/biblio/1409050},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 23,

  volume       = 139,

  place        = {United States},

  year         = {Mon Dec 16 00:00:00 EST 2013},

  month        = {Mon Dec 16 00:00:00 EST 2013}

}

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Works referenced in this record:

Unravelling combustion mechanisms through a quantitative understanding of elementary reactions
journal, January 2005

Miller, James A.; Pilling, Michael J.; Troe, Jürgen
Proceedings of the Combustion Institute, Vol. 30, Issue 1
https://doi.org/10.1016/j.proci.2004.08.281

The Recombination of Propargyl Radicals: Solving the Master Equation
journal, August 2001

Miller, James A.; Klippenstein, Stephen J.
The Journal of Physical Chemistry A, Vol. 105, Issue 30
https://doi.org/10.1021/jp0102973

Slit Discharge IR Spectroscopy of a Jet-Cooled Cyclopropyl Radical: Structure and Intramolecular Tunneling Dynamics ^†
journal, March 2006

Dong, Feng; Davis, Scott; Nesbitt, David J.
The Journal of Physical Chemistry A, Vol. 110, Issue 9
https://doi.org/10.1021/jp053994u

The Growth of HF Polymers in Helium Nanodroplets: Probing the Barriers to Ring Insertion
journal, April 2003

Douberly, G. E.; Miller, R. E.
The Journal of Physical Chemistry B, Vol. 107, Issue 19
https://doi.org/10.1021/jp022360+

Successive capture and coagulation of atoms and molecules to small clusters in large liquid helium clusters
journal, May 1995

Lewerenz, M.; Schilling, B.; Toennies, J. P.
The Journal of Chemical Physics, Vol. 102, Issue 20
https://doi.org/10.1063/1.469231

Density of states and evaporation rate of helium clusters
journal, September 1990

Brink, D. M.; Stringari, S.
Zeitschrift f�r Physik D Atoms, Molecules and Clusters, Vol. 15, Issue 3
https://doi.org/10.1007/BF01437187

Thermochemistry of the benzyl and allyl radicals and ions
journal, November 1996

Ellison, G. Barney; Davico, Gustavo E.; Bierbaum, Veronica M.
International Journal of Mass Spectrometry and Ion Processes, Vol. 156, Issue 1-2
https://doi.org/10.1016/S0168-1176(96)04383-2

Direct observation of the equilibrium between allyl radicals, oxygen, and allylperoxy radicals
journal, June 1981

Ruiz, Rennie P.; Bayes, Kyle D.; Macpherson, Martyn T.
The Journal of Physical Chemistry, Vol. 85, Issue 12
https://doi.org/10.1021/j150612a003

Using He droplets for measurements of interconversion enthalpy of conformers in 2-chloroethanol
journal, April 2009

Skvortsov, Dmitry S.; Vilesov, Andrey F.
The Journal of Chemical Physics, Vol. 130, Issue 15
https://doi.org/10.1063/1.3111969

High-resolution infrared spectra of jet-cooled allyl radical (CH2–CH–CH2): ν2, ν3, and ν14 C–H stretch vibrations
journal, April 2002

Han, Jia-xiang; Utkin, Yu. G.; Chen, Hong-bing
The Journal of Chemical Physics, Vol. 116, Issue 15
https://doi.org/10.1063/1.1459417

Aggregation-Induced Chemical Reactions: Acid Dissociation in Growing Water Clusters
journal, March 2011

Forbert, Harald; Masia, Marco; Kaczmarek-Kedziera, Anna
Journal of the American Chemical Society, Vol. 133, Issue 11
https://doi.org/10.1021/ja1099209

A new scattering deflection method for determining and selecting the sizes of large liquid clusters of 4He
journal, April 1993

Lewerenz, M.; Schilling, B.; Toennies, J. P.
Chemical Physics Letters, Vol. 206, Issue 1-4
https://doi.org/10.1016/0009-2614(93)85569-A

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
https://doi.org/10.1063/1.1418746

Polarized Infrared Absorption Spectra of Matrix-Isolated Allyl Radicals
journal, August 2001

Nandi, Sreela; Arnold, Pamela A.; Carpenter, Barry K.
The Journal of Physical Chemistry A, Vol. 105, Issue 32
https://doi.org/10.1021/jp011163s

Multiple tautomers of cytosine identified and characterized by infrared laser spectroscopy in helium nanodroplets: probing structure using vibrational transition moment angles
journal, December 2004

Choi, M. Y.; Dong, F.; Miller, R. E.
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 363, Issue 1827
https://doi.org/10.1098/rsta.2004.1499

Kinetic ( T = 201–298 K) and Equilibrium ( T = 320–420 K) Measurements of the C ₃ H ₅ + O ₂ ⇆ C ₃ H ₅ O ₂ Reaction
journal, April 2012

Rissanen, Matti P.; Amedro, Damien; Eskola, Arkke J.
The Journal of Physical Chemistry A, Vol. 116, Issue 16
https://doi.org/10.1021/jp209977h

Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels
journal, October 1992

Miller, James A.; Melius, Carl F.
Combustion and Flame, Vol. 91, Issue 1
https://doi.org/10.1016/0010-2180(92)90124-8

Thermochemical and kinetic analysis of the allyl radical with O2 reaction system
journal, January 2005

Lee, Jongwoo; Bozzelli, Joseph W.
Proceedings of the Combustion Institute, Vol. 30, Issue 1
https://doi.org/10.1016/j.proci.2004.08.092

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
https://doi.org/10.1063/1.4764298

Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H ₂ CCHCH ₂ ) Self-Reaction ^†
journal, October 2008

Selby, Talitha M.; Meloni, Giovanni; Goulay, Fabien
The Journal of Physical Chemistry A, Vol. 112, Issue 39
https://doi.org/10.1021/jp802330k

Gas Phase Kinetics and Equilibrium of Allyl Radical Reactions with NO and NO ₂
journal, January 2013

Rissanen, Matti P.; Amedro, Damien; Krasnoperov, Lev
The Journal of Physical Chemistry A, Vol. 117, Issue 5
https://doi.org/10.1021/jp308621f

High resolution vibronic spectra of the amino acids tryptophan and tyrosine in 0.38 K cold helium droplets
journal, January 1999

Lindinger, Albrecht; Toennies, J. Peter; Vilesov, Andrei F.
The Journal of Chemical Physics, Vol. 110, Issue 3
https://doi.org/10.1063/1.478018

A second-order perturbation theory route to vibrational averages and transition properties of molecules: General formulation and application to infrared and vibrational circular dichroism spectroscopies
journal, March 2012

Bloino, Julien; Barone, Vincenzo
The Journal of Chemical Physics, Vol. 136, Issue 12
https://doi.org/10.1063/1.3695210

Propargyl + O ₂ Reaction in Helium Droplets: Entrance Channel Barrier or Not?
journal, September 2013

Moradi, Christopher P.; Morrison, Alexander M.; Klippenstein, Stephen J.
The Journal of Physical Chemistry A, Vol. 117, Issue 50
https://doi.org/10.1021/jp407652f

Systematics of pure and doped ${}^{4}{He}$ clusters
journal, October 1995

Chin, S. A.; Krotscheck, E.
Physical Review B, Vol. 52, Issue 14
https://doi.org/10.1103/PhysRevB.52.10405

Anharmonic vibrational properties by a fully automated second-order perturbative approach
journal, January 2005

Barone, Vincenzo
The Journal of Chemical Physics, Vol. 122, Issue 1
https://doi.org/10.1063/1.1824881

The isomers of HF–HCN formed in helium nanodroplets: Infrared spectroscopy and ab initio calculations
journal, January 2005

Douberly, G. E.; Miller, R. E.
The Journal of Chemical Physics, Vol. 122, Issue 2
https://doi.org/10.1063/1.1828047

Four Tautomers of Isolated Guanine from Infrared Laser Spectroscopy in Helium Nanodroplets
journal, June 2006

Choi, Myong Yong; Miller, Roger E.
Journal of the American Chemical Society, Vol. 128, Issue 22
https://doi.org/10.1021/ja060741l

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
https://doi.org/10.1063/1.4802767

Kinetics of polyatomic free radicals produced by laser photolysis. 4. Study of the equilibrium isopropyl + oxygen .tautm. isopropylperoxy between 592 and 692 K
journal, April 1985

Slagle, Irene R.; Ratajczak, Emil; Heaven, Michael C.
Journal of the American Chemical Society, Vol. 107, Issue 7
https://doi.org/10.1021/ja00293a006

Reaction mechanism of soot formation in flames
journal, February 2002

Frenklach, Michael
Physical Chemistry Chemical Physics, Vol. 4, Issue 11
https://doi.org/10.1039/b110045a

Reactions between Resonance-Stabilized Radicals: Propargyl + Allyl ^†
journal, April 2010

Miller, James A.; Klippenstein, Stephen J.; Georgievskii, Yuri
The Journal of Physical Chemistry A, Vol. 114, Issue 14
https://doi.org/10.1021/jp910604b

Formation and consumption of single-ring aromatic hydrocarbons and their precursors in premixed acetylene, ethylene and benzene flamesElectronic supplementary information (ESI) available: Thermodynamic and kinetic property data. See http://www.rsc.org/suppdata/cp/b1/b110089k/
journal, April 2002

Richter, Henning; Howard, Jack B.
Physical Chemistry Chemical Physics, Vol. 4, Issue 11
https://doi.org/10.1039/b110089k

Infrared spectroscopy and structures of Ar[sub n]–HF in liquid helium nanodroplets
journal, January 2001

Nauta, K.; Miller, R. E.
The Journal of Chemical Physics, Vol. 115, Issue 22
https://doi.org/10.1063/1.1392378

Rotationally Resolved Spectroscopy of S $F_{6}$ 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
https://doi.org/10.1103/PhysRevLett.75.1566

Direct determination of the equilibrium constant and thermodynamic parameters for the reaction. C3H5+ O2? C3H5O2
journal, January 1982

Morgan, Carol A.; Pilling, Michael J.; Tulloch, James M.
Journal of the Chemical Society, Faraday Transactions 2, Vol. 78, Issue 8
https://doi.org/10.1039/f29827801323

Association rate constants for reactions between resonance-stabilized radicals: C3H3 + C3H3, C3H3 + C3H5, and C3H5 + C3H5
journal, January 2007

Georgievskii, Yuri; Miller, James A.; Klippenstein, Stephen J.
Physical Chemistry Chemical Physics, Vol. 9, Issue 31
https://doi.org/10.1039/b703261g

Cavity ringdown spectroscopy of the NIR <mml:math altimg="si112.gif" display="inline" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mi>A</mml:mi></mml:mrow><mml:mrow><mml:mo stretchy="true">∼</mml:mo></mml:mrow></mml:mover><mml:mo>-</mml:mo><mml:mover accent="true"><mml:mrow><mml:mi>X</mml:mi></mml:mrow><mml:mrow><mml:mo stretchy="true">∼</mml:mo></mml:mrow></mml:mover></mml:mrow></mml:math> electronic transition of allyl peroxy radical (H2CCH–CH2OO·)
journal, May 2010

Thomas, Phillip S.; Miller, Terry A.
Chemical Physics Letters, Vol. 491, Issue 4-6
https://doi.org/10.1016/j.cplett.2010.03.073

Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds
journal, June 1991

Curtiss, Larry A.; Raghavachari, Krishnan; Trucks, Gary W.
The Journal of Chemical Physics, Vol. 94, Issue 11
https://doi.org/10.1063/1.460205

Line broadening in electronic spectra of anthracene derivatives inside superfluid helium nanodroplets
journal, September 2010

Pentlehner, D.; Greil, Ch.; Dick, B.
The Journal of Chemical Physics, Vol. 133, Issue 11
https://doi.org/10.1063/1.3479583

Infrared diode laser spectroscopy of the allyl radical. The ν ₁₁ band
journal, September 1992

Hirota, Eizi; Yamada, Chikashi; Okunishi, Misaki
The Journal of Chemical Physics, Vol. 97, Issue 5
https://doi.org/10.1063/1.463037

Modeling the rich combustion of aliphatic hydrocarbons
journal, March 2000

D’Anna, A.; violi, A.; D’Alessio, A.
Combustion and Flame, Vol. 121, Issue 3
https://doi.org/10.1016/S0010-2180(99)00163-7

Excitation and ionization of ⁴ He clusters by electrons
journal, December 1991

Buchenau, H.; Toennies, J. P.; Northby, J. A.
The Journal of Chemical Physics, Vol. 95, Issue 11
https://doi.org/10.1063/1.461294

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
https://doi.org/10.1002/anie.200300611

The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations
journal, May 2013

Raston, Paul L.; Agarwal, Jay; Turney, Justin M.
The Journal of Chemical Physics, Vol. 138, Issue 19
https://doi.org/10.1063/1.4804435

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
https://doi.org/10.1063/1.1484104

Hydrocarbon radical reactions with oxygen: comparison of allyl, formyl, and vinyl to ethyl
journal, April 1993

Bozzelli, Joseph W.; Dean, Anthony M.
The Journal of Physical Chemistry, Vol. 97, Issue 17
https://doi.org/10.1021/j100119a030

The rotationally resolved infrared spectrum of the ν1 stretch of the allyl radical
journal, November 1998

DeSain, J. D.; Thompson, R. I.; Sharma, S. D.
The Journal of Chemical Physics, Vol. 109, Issue 18
https://doi.org/10.1063/1.477426

High-resolution infrared spectroscopy of jet-cooled allyl radical (CH2–CH–CH2): In-phase (ν1) and out-of-phase (ν13) antisymmetric CH2 stretching vibrations
journal, November 1998

Uy, Dairene; Davis, Scott; Nesbitt, David J.
The Journal of Chemical Physics, Vol. 109, Issue 18
https://doi.org/10.1063/1.477425

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
https://doi.org/10.1080/01442350600625092

Acetylene⋅⋅⋅Furan Trimer Formation at 0.37 K as a Model for Ultracold Aggregation of Non- and Weakly Polar Molecules
journal, May 2011

Metzelthin, Anja; Sánchez-García, Elsa; Birer, Özgür
ChemPhysChem, Vol. 12, Issue 10
https://doi.org/10.1002/cphc.201001040

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
https://doi.org/10.1063/1.4776179

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Title: Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals

Abstract

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Helium nanodroplet isolation rovibrational spectroscopy: Methods and recent results journal, January 2001

Polarized Infrared Absorption Spectra of Matrix-Isolated Allyl Radicals journal, August 2001

Multiple tautomers of cytosine identified and characterized by infrared laser spectroscopy in helium nanodroplets: probing structure using vibrational transition moment angles journal, December 2004

Kinetic ( T = 201–298 K) and Equilibrium ( T = 320–420 K) Measurements of the C 3 H 5 + O 2 ⇆ C 3 H 5 O 2 Reaction journal, April 2012

Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels journal, October 1992

Thermochemical and kinetic analysis of the allyl radical with O2 reaction system journal, January 2005

Infrared spectroscopy of HOOO and DOOO in 4 He nanodroplets journal, November 2012

Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H 2 CCHCH 2 ) Self-Reaction † journal, October 2008

Gas Phase Kinetics and Equilibrium of Allyl Radical Reactions with NO and NO 2 journal, January 2013

High resolution vibronic spectra of the amino acids tryptophan and tyrosine in 0.38 K cold helium droplets journal, January 1999

A second-order perturbation theory route to vibrational averages and transition properties of molecules: General formulation and application to infrared and vibrational circular dichroism spectroscopies journal, March 2012

Propargyl + O 2 Reaction in Helium Droplets: Entrance Channel Barrier or Not? journal, September 2013

Systematics of pure and doped He 4 clusters journal, October 1995

Anharmonic vibrational properties by a fully automated second-order perturbative approach journal, January 2005

The isomers of HF–HCN formed in helium nanodroplets: Infrared spectroscopy and ab initio calculations journal, January 2005

Four Tautomers of Isolated Guanine from Infrared Laser Spectroscopy in Helium Nanodroplets journal, June 2006

Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4 He nanodroplets journal, May 2013

Kinetics of polyatomic free radicals produced by laser photolysis. 4. Study of the equilibrium isopropyl + oxygen .tautm. isopropylperoxy between 592 and 692 K journal, April 1985

Reaction mechanism of soot formation in flames journal, February 2002

Reactions between Resonance-Stabilized Radicals: Propargyl + Allyl † journal, April 2010

Formation and consumption of single-ring aromatic hydrocarbons and their precursors in premixed acetylene, ethylene and benzene flamesElectronic supplementary information (ESI) available: Thermodynamic and kinetic property data. See http://www.rsc.org/suppdata/cp/b1/b110089k/ journal, April 2002

Infrared spectroscopy and structures of Ar[sub n]–HF in liquid helium nanodroplets journal, January 2001

Rotationally Resolved Spectroscopy of S F 6 in Liquid Helium Clusters: A Molecular Probe of Cluster Temperature journal, August 1995

Direct determination of the equilibrium constant and thermodynamic parameters for the reaction. C3H5+ O2? C3H5O2 journal, January 1982

Association rate constants for reactions between resonance-stabilized radicals: C3H3 + C3H3, C3H3 + C3H5, and C3H5 + C3H5 journal, January 2007

Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds journal, June 1991

Line broadening in electronic spectra of anthracene derivatives inside superfluid helium nanodroplets journal, September 2010

Infrared diode laser spectroscopy of the allyl radical. The ν 11 band journal, September 1992

Modeling the rich combustion of aliphatic hydrocarbons journal, March 2000

Excitation and ionization of 4 He clusters by electrons journal, December 1991

Superfluid Helium Droplets: A Uniquely Cold Nanomatrix for Molecules and Molecular Complexes journal, May 2004

The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations journal, May 2013

Free radicals in superfluid liquid helium nanodroplets: A pyrolysis source for the production of propargyl radical journal, July 2002

Hydrocarbon radical reactions with oxygen: comparison of allyl, formyl, and vinyl to ethyl journal, April 1993

The rotationally resolved infrared spectrum of the ν1 stretch of the allyl radical journal, November 1998

High-resolution infrared spectroscopy of jet-cooled allyl radical (CH2–CH–CH2): In-phase (ν1) and out-of-phase (ν13) antisymmetric CH2 stretching vibrations journal, November 1998

Infrared spectroscopy of helium nanodroplets: novel methods for physics and chemistry journal, January 2006

Acetylene⋅⋅⋅Furan Trimer Formation at 0.37 K as a Model for Ultracold Aggregation of Non- and Weakly Polar Molecules journal, May 2011

Automation of an “Aculight” continuous-wave optical parametric oscillator journal, January 2013

Infrared spectroscopy in superfluid helium droplets journal, December 2018

Unravelling combustion mechanisms through a quantitative understanding of elementary reactions
journal, January 2005

The Recombination of Propargyl Radicals: Solving the Master Equation
journal, August 2001

Slit Discharge IR Spectroscopy of a Jet-Cooled Cyclopropyl Radical: Structure and Intramolecular Tunneling Dynamics ^†
journal, March 2006

The Growth of HF Polymers in Helium Nanodroplets: Probing the Barriers to Ring Insertion
journal, April 2003

Successive capture and coagulation of atoms and molecules to small clusters in large liquid helium clusters
journal, May 1995

Density of states and evaporation rate of helium clusters
journal, September 1990

Thermochemistry of the benzyl and allyl radicals and ions
journal, November 1996

Direct observation of the equilibrium between allyl radicals, oxygen, and allylperoxy radicals
journal, June 1981

Using He droplets for measurements of interconversion enthalpy of conformers in 2-chloroethanol
journal, April 2009

High-resolution infrared spectra of jet-cooled allyl radical (CH2–CH–CH2): ν2, ν3, and ν14 C–H stretch vibrations
journal, April 2002

Aggregation-Induced Chemical Reactions: Acid Dissociation in Growing Water Clusters
journal, March 2011

A new scattering deflection method for determining and selecting the sizes of large liquid clusters of 4He
journal, April 1993

Helium nanodroplet isolation rovibrational spectroscopy: Methods and recent results
journal, January 2001

Polarized Infrared Absorption Spectra of Matrix-Isolated Allyl Radicals
journal, August 2001

Multiple tautomers of cytosine identified and characterized by infrared laser spectroscopy in helium nanodroplets: probing structure using vibrational transition moment angles
journal, December 2004

Kinetic ( T = 201–298 K) and Equilibrium ( T = 320–420 K) Measurements of the C ₃ H ₅ + O ₂ ⇆ C ₃ H ₅ O ₂ Reaction
journal, April 2012

Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels
journal, October 1992

Thermochemical and kinetic analysis of the allyl radical with O2 reaction system
journal, January 2005

Infrared spectroscopy of HOOO and DOOO in ⁴ He nanodroplets
journal, November 2012

Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H ₂ CCHCH ₂ ) Self-Reaction ^†
journal, October 2008

Gas Phase Kinetics and Equilibrium of Allyl Radical Reactions with NO and NO ₂
journal, January 2013

High resolution vibronic spectra of the amino acids tryptophan and tyrosine in 0.38 K cold helium droplets
journal, January 1999

A second-order perturbation theory route to vibrational averages and transition properties of molecules: General formulation and application to infrared and vibrational circular dichroism spectroscopies
journal, March 2012

Propargyl + O ₂ Reaction in Helium Droplets: Entrance Channel Barrier or Not?
journal, September 2013

Systematics of pure and doped ${}^{4}{He}$ clusters
journal, October 1995

Anharmonic vibrational properties by a fully automated second-order perturbative approach
journal, January 2005

The isomers of HF–HCN formed in helium nanodroplets: Infrared spectroscopy and ab initio calculations
journal, January 2005

Four Tautomers of Isolated Guanine from Infrared Laser Spectroscopy in Helium Nanodroplets
journal, June 2006

Infrared spectroscopy and tunneling dynamics of the vinyl radical in ⁴ He nanodroplets
journal, May 2013

Kinetics of polyatomic free radicals produced by laser photolysis. 4. Study of the equilibrium isopropyl + oxygen .tautm. isopropylperoxy between 592 and 692 K
journal, April 1985

Reaction mechanism of soot formation in flames
journal, February 2002

Reactions between Resonance-Stabilized Radicals: Propargyl + Allyl ^†
journal, April 2010

Formation and consumption of single-ring aromatic hydrocarbons and their precursors in premixed acetylene, ethylene and benzene flamesElectronic supplementary information (ESI) available: Thermodynamic and kinetic property data. See http://www.rsc.org/suppdata/cp/b1/b110089k/
journal, April 2002

Infrared spectroscopy and structures of Ar[sub n]–HF in liquid helium nanodroplets
journal, January 2001

Rotationally Resolved Spectroscopy of S $F_{6}$ in Liquid Helium Clusters: A Molecular Probe of Cluster Temperature
journal, August 1995

Direct determination of the equilibrium constant and thermodynamic parameters for the reaction. C3H5+ O2? C3H5O2
journal, January 1982

Association rate constants for reactions between resonance-stabilized radicals: C3H3 + C3H3, C3H3 + C3H5, and C3H5 + C3H5
journal, January 2007

Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds
journal, June 1991

Line broadening in electronic spectra of anthracene derivatives inside superfluid helium nanodroplets
journal, September 2010

Infrared diode laser spectroscopy of the allyl radical. The ν ₁₁ band
journal, September 1992

Modeling the rich combustion of aliphatic hydrocarbons
journal, March 2000

Excitation and ionization of ⁴ He clusters by electrons
journal, December 1991

Superfluid Helium Droplets: A Uniquely Cold Nanomatrix for Molecules and Molecular Complexes
journal, May 2004

The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations
journal, May 2013

Free radicals in superfluid liquid helium nanodroplets: A pyrolysis source for the production of propargyl radical
journal, July 2002

Hydrocarbon radical reactions with oxygen: comparison of allyl, formyl, and vinyl to ethyl
journal, April 1993

The rotationally resolved infrared spectrum of the ν1 stretch of the allyl radical
journal, November 1998

High-resolution infrared spectroscopy of jet-cooled allyl radical (CH2–CH–CH2): In-phase (ν1) and out-of-phase (ν13) antisymmetric CH2 stretching vibrations
journal, November 1998

Infrared spectroscopy of helium nanodroplets: novel methods for physics and chemistry
journal, January 2006

Acetylene⋅⋅⋅Furan Trimer Formation at 0.37 K as a Model for Ultracold Aggregation of Non- and Weakly Polar Molecules
journal, May 2011

Automation of an “Aculight” continuous-wave optical parametric oscillator
journal, January 2013

Infrared spectroscopy in superfluid helium droplets
journal, December 2018