Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl, and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations

Brown, Alaina R.; Franke, Peter R.; Douberly, Gary E.

doi:10.1021/acs.jpca.7b07852

Title: Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl, and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations

Journal Article · Fri Sep 22 00:00:00 EDT 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.7b07852· OSTI ID:1409066

Brown, Alaina R. ^[1]; Franke, Peter R. ^[1];

^[1]

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

Gas-phase cyclobutyl radical (*C₄H₇) is produced via pyrolysis of cyclobutylmethyl nitrite (C₄H₇(CH₂)ONO). Other (C₄H₇)-C-center dot radicals, such as 1-methylallyl and allylcarbinyl, are similarly produced from nitrite precursors. Nascent radicals are promptly solvated in liquid He droplets, allowing for the acquisition of infrared spectra in the CH stretching region. For the cyclobutyl and 1-methylallyl radicals, anharmonic frequencies are predicted by VPT2+K simulations based upon a hybrid CCSD(T) force field with quadratic (cubic and quartic) force constants computed using the ANO1 (ANO0) basis set. A density functional theoretical method is used to compute the force field for the allylcarbinyl radical. For all *C₄H₇ radicals, resonance polyads in the 2800-3000 cm^-1 region appear as a result of anharmonic coupling between the CH stretching fundamentals and CH, bend overtones and combinations. Upon pyrolysis of the cyclobutylmethyl nitrite precursor to produce the cyclobutyl radical, an approximately 2-fold increase in the source temperature leads to the appearance of spectral signatures that can be assigned to 1-methylallyl and 1,3-butadiene. On the basis of a previously reported *C₄H₇ potential energy surface, this result is interpreted as evidence for the unimolecular decomposition of the cyclobutyl radical via ring opening, prior to it being captured by helium droplets. On the *C₄H₇ potential surface, 1,3-butadiene is formed from cyclobutyl ring opening and H atom loss, and the 1-methylallyl radical is the most energetically stable intermediate along the decomposition pathway. Here, the allylcarbinyl radical is a higher-energy (C₄H₇)-C-center dot intermediate along the ring-opening path, and the spectral signatures of this radical are not observed under the same conditions that produce 1-methylallyl and 1,3-butadiene from the unimolecular decomposition of cyclobutyl.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008086

OSTI ID:: 1409066

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 121, Issue 40; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 10 works

Citation information provided by
Web of Science

References (61)

Study of combustion intermediates in fuel-rich methyl methacrylate flame with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry Lin, Zhenkun; Wang, Tianfang; Han, Donglin Rapid Communications in Mass Spectrometry, Vol. 23, Issue 1 https://doi.org/10.1002/rcm.3838	journal	January 2009
Identification of combustion intermediates in isomeric fuel-rich premixed butanol–oxygen flames at low pressure Yang, B.; Oswald, P.; Li, Y. Combustion and Flame, Vol. 148, Issue 4 https://doi.org/10.1016/j.combustflame.2006.12.001	journal	March 2007
Pyrolysis of Methyl tert -Butyl Ether (MTBE). 1. Experimental Study with Molecular-Beam Mass Spectrometry and Tunable Synchrotron VUV Photoionization Zhang, Taichang; Wang, Jing; Yuan, Tao The Journal of Physical Chemistry A, Vol. 112, Issue 42 https://doi.org/10.1021/jp803622w	journal	October 2008
Propyne Pyrolysis in a Flow Reactor: An Experimental, RRKM, and Detailed Kinetic Modeling Study Davis, Scott G.; Law, Chung K.; Wang, Hai The Journal of Physical Chemistry A, Vol. 103, Issue 30 https://doi.org/10.1021/jp982762a	journal	July 1999
Reaction Mechanism and Product Branching Ratios of the CH + C ₃ H ₆ Reaction: A Theoretical Study Ribeiro, Joao Marcelo; Mebel, Alexander M. The Journal of Physical Chemistry A, Vol. 120, Issue 11 https://doi.org/10.1021/acs.jpca.5b12588	journal	March 2016
Superfluid Helium Droplets: A Uniquely Cold Nanomatrix for Molecules and Molecular Complexes Toennies, J. Peter; Vilesov, Andrey F. Angewandte Chemie International Edition, Vol. 43, Issue 20 https://doi.org/10.1002/anie.200300611	journal	May 2004
Infrared spectroscopy of helium nanodroplets: novel methods for physics and chemistry 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	journal	January 2006
Photoelectron spectroscopy of isomeric C4H7 radicals. Implications for the thermochemistry and structures of the radicals and their corresponding carbonium ions Schultz, Jocelyn C.; Houle, F. A.; Beauchamp, J. L. Journal of the American Chemical Society, Vol. 106, Issue 24 https://doi.org/10.1021/ja00336a008	journal	November 1984
Free Radicals by Mass Spectrometry. XXIV. Ionization Potentials of Cycloalkyl Free Radicals and Cycloalkanes Pottie, R. F.; Harrison, A. G.; Lossing, F. P. Journal of the American Chemical Society, Vol. 83, Issue 15 https://doi.org/10.1021/ja01476a009	journal	August 1961
Experimental evidence for the existence of gaseous cyclobutyl cation Bowen, Richard D.; Williams, Dudley H.; Schwarz, Helmut Journal of the Chemical Society, Chemical Communications, Issue 6 https://doi.org/10.1039/c39790000261	journal	January 1979
Photolysis of Mixtures of Cyclobutane and Acetone‐ d ₆ . Reactions of the Cyclobutyl Radical Gordon, Alvin S.; Smith, S. Ruven; Drew, Charles M. The Journal of Chemical Physics, Vol. 36, Issue 3 https://doi.org/10.1063/1.1732616	journal	February 1962
Pyrolyses of azoalkanes. photoelectron spectra of some hydrocarbon radicals Bischof, P.; Friedrich, G. Tetrahedron Letters, Vol. 26, Issue 20 https://doi.org/10.1016/S0040-4039(00)94844-5	journal	January 1985
Photodissociation of Cyclobutyl Bromide at 234 nm Studied Using Velocity Map Imaging ^† Liu, Yi; Lau, Kai-Chung; Butler, Laurie J. The Journal of Physical Chemistry A, Vol. 110, Issue 16 https://doi.org/10.1021/jp056255m	journal	April 2006
Proof of existence of cyclic C4H7+ ions in the dilute gas state Cacace, Fulvio; Speranza, Maurizio Journal of the American Chemical Society, Vol. 101, Issue 6 https://doi.org/10.1021/ja00500a036	journal	March 1979
Free Radicals by Mass Spectrometry. XLV. Ionization Potentials and Heats of Formation of C ₃ H ₃ , C ₃ H ₅ , and C ₄ H ₇ Radicals and Ions Lossing, F. P. Canadian Journal of Chemistry, Vol. 50, Issue 24 https://doi.org/10.1139/v72-629	journal	December 1972
Theoretical prediction of the ionization energies of the C4H7 radicals: 1-Methylallyl, 2-methylallyl, cyclopropylmethyl, and cyclobutyl radicals Lau, Kai-Chung; Zheng, Wenxu; Wong, Ning-Bew The Journal of Chemical Physics, Vol. 127, Issue 15 https://doi.org/10.1063/1.2774972	journal	October 2007
Calculation of isotropic hyperfine coupling constants in cyclobutyl radical Zhidomirov, G. M.; Abronin, I. A.; Micheikin, I. D. Journal of Magnetic Resonance (1969), Vol. 17, Issue 2 https://doi.org/10.1016/0022-2364(75)90174-2	journal	February 1975
Photodissociation of 1-bromo-2-butene, 4-bromo-1-butene, and cyclopropylmethyl bromide at 234nm studied using velocity map imaging Lau, Kai-Chung; Liu, Yi; Butler, Laurie J. The Journal of Chemical Physics, Vol. 125, Issue 14 https://doi.org/10.1063/1.2353836	journal	October 2006
Isomerization of gas-phase hydrocarbon ions. Radical trapping. 3 McEwen, C. N.; Rudat, M. A. Journal of the American Chemical Society, Vol. 103, Issue 15 https://doi.org/10.1021/ja00405a011	journal	July 1981
Allylcarbinyl-cyclopropylcarbinyl rearrangement Effio, A.; Griller, D.; Ingold, K. U. Journal of the American Chemical Society, Vol. 102, Issue 5 https://doi.org/10.1021/ja00525a051	journal	February 1980
Conformations and rotation barriers in allylcarbinyl radicals by electron spin resonance Chen, Kuang S.; Edge, David J.; Kochi, Jay K. Journal of the American Chemical Society, Vol. 95, Issue 21 https://doi.org/10.1021/ja00802a026	journal	October 1973
Rearrangement of the allylcarbinyl radical Montgomery, Lawrence K.; Matt, John W. Journal of the American Chemical Society, Vol. 89, Issue 12 https://doi.org/10.1021/ja00988a045	journal	June 1967
Homoallylic free-radical rearrangements. IV. Rearrangements of the allylcarbinyl radicals Montgomery, Lawrence K.; Matt, John W. Journal of the American Chemical Society, Vol. 89, Issue 25 https://doi.org/10.1021/ja01001a031	journal	December 1967
Infrared absorption of trans -1-chloromethylallyl and trans -1-methylallyl radicals produced in photochemical reactions of trans -1,3-butadiene and Cℓ ₂ in solid para -hydrogen Bahou, Mohammed; Wu, Jen-Yu; Tanaka, Keiichi The Journal of Chemical Physics, Vol. 137, Issue 8 https://doi.org/10.1063/1.4745075	journal	August 2012
Theoretical Study of the Straight-Chain C ₄ H ₇ Radical Isomers and Their Dissociation and Isomerization Transition States Miller, Johanna L. The Journal of Physical Chemistry A, Vol. 108, Issue 12 https://doi.org/10.1021/jp0374511	journal	March 2004
Threshold Photoelectron Spectra of Combustion Relevant C ₄ H ₅ and C ₄ H ₇ Isomers Lang, Melanie; Holzmeier, Fabian; Hemberger, Patrick The Journal of Physical Chemistry A, Vol. 119, Issue 17 https://doi.org/10.1021/acs.jpca.5b02153	journal	April 2015
Probing for non-statistical effects in dissociation of the 1-methylallyl radical Gasser, Michael; Frey, Jann A.; Hostettler, Jonas M. Chem. Commun., Vol. 47, Issue 1 https://doi.org/10.1039/C0CC01899F	journal	January 2011
Thermochemistry and Kinetics of the Reaction of 1-Methylallyl Radicals with Molecular Oxygen Knyazev, Vadim D.; Slagle, Irene R. The Journal of Physical Chemistry A, Vol. 102, Issue 45 https://doi.org/10.1021/jp982923a	journal	November 1998
Resonance Raman Spectroscopy of the 1-Methylallyl Radical Tarrant, Darcy H.; Getty, James D.; Liu, Xianming The Journal of Physical Chemistry, Vol. 100, Issue 19 https://doi.org/10.1021/jp9526253	journal	January 1996
Cis–Trans Isomerization of Chemically Activated 1-Methylallyl Radical and Fate of the Resulting 2-Buten-1-peroxy Radical Dibble, Theodore S.; Sha, Yuan; Thornton, William F. The Journal of Physical Chemistry A, Vol. 116, Issue 29 https://doi.org/10.1021/jp303652x	journal	July 2012
The kinetics of the cis–trans-isomerisation of the 1-methylallyl radical. A new technique for the study of unimolecular radical reactions Gorton, P. J.; Walsh, R. J. Chem. Soc., Chem. Commun., Issue 13 https://doi.org/10.1039/C39720000783	journal	January 1972
Formation of gas-phase methylallyl radicals during the oxidation of 1-butene and isobutylene over bismuth oxide Driscoll, Daniel J.; Martir, Wilson.; Lunsford, Jack H. The Journal of Physical Chemistry, Vol. 91, Issue 13 https://doi.org/10.1021/j100297a024	journal	June 1987
Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Ethylene ^† Ismail, Huzeifa; Goldsmith, C. Franklin; Abel, Paul R. The Journal of Physical Chemistry A, Vol. 111, Issue 29 https://doi.org/10.1021/jp071041l	journal	July 2007
A new scattering deflection method for determining and selecting the sizes of large liquid clusters of 4He 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	journal	April 1993
Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals Leavitt, Christopher M.; Moradi, Christopher P.; Acrey, Bradley W. The Journal of Chemical Physics, Vol. 139, Issue 23 https://doi.org/10.1063/1.4844175	journal	December 2013
Propargyl + O ₂ Reaction in Helium Droplets: Entrance Channel Barrier or Not? 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	journal	September 2013
The ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations Raston, Paul L.; Agarwal, Jay; Turney, Justin M. The Journal of Chemical Physics, Vol. 138, Issue 19 https://doi.org/10.1063/1.4804435	journal	May 2013
Infrared laser spectroscopy of the n -propyl and i -propyl radicals: Stretch-bend Fermi coupling in the alkyl CH stretch region Franke, Peter R.; Tabor, Daniel P.; Moradi, Christopher P. The Journal of Chemical Physics, Vol. 145, Issue 22 https://doi.org/10.1063/1.4971239	journal	December 2016
Automation of an “Aculight” continuous-wave optical parametric oscillator Morrison, Alexander M.; Liang, Tao; Douberly, Gary E. Review of Scientific Instruments, Vol. 84, Issue 1 https://doi.org/10.1063/1.4776179	journal	January 2013
Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H ₂ O and OH(D ₂ O) _n ( n = 1-3) Hernandez, Federico J.; Brice, Joseph T.; Leavitt, Christopher M. The Journal of Chemical Physics, Vol. 143, Issue 16 https://doi.org/10.1063/1.4933432	journal	October 2015
A fifth-order perturbation comparison of electron correlation theories Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A. Chemical Physics Letters, Vol. 157, Issue 6 https://doi.org/10.1016/S0009-2614(89)87395-6	journal	May 1989
A comparison of the efficiency and accuracy of the quadratic configuration interaction (QCISD), coupled cluster (CCSD), and Brueckner coupled cluster (BCCD) methods Hampel, Claudia; Peterson, Kirk A.; Werner, Hans-Joachim Chemical Physics Letters, Vol. 190, Issue 1-2 https://doi.org/10.1016/0009-2614(92)86093-W	journal	February 1992
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients Watts, John D.; Gauss, Jürgen; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 98, Issue 11 https://doi.org/10.1063/1.464480	journal	June 1993
Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories Deegan, Miles J. O.; Knowles, Peter J. Chemical Physics Letters, Vol. 227, Issue 3 https://doi.org/10.1016/0009-2614(94)00815-9	journal	September 1994
Why CCSD(T) works: a different perspective Stanton, John F. Chemical Physics Letters, Vol. 281, Issue 1-3 https://doi.org/10.1016/S0009-2614(97)01144-5	journal	December 1997
General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms Almlöf, Jan; Taylor, Peter R. The Journal of Chemical Physics, Vol. 86, Issue 7 https://doi.org/10.1063/1.451917	journal	April 1987
A systematic study of molecular vibrational anharmonicity and vibration—rotation interaction by self-consistent-field higher-derivative methods. Asymmetric top molecules Clabo, D. Allen; Allen, Wesley D.; Remington, Richard B. Chemical Physics, Vol. 123, Issue 2 https://doi.org/10.1016/0301-0104(88)87271-9	journal	July 1988
Calculated stretching overtone levels and Darling–Dennison resonances in water: a triumph of simple theoretical approaches Matthews, Devin A.; Vázquez, Juana; Stanton, John F. Molecular Physics, Vol. 105, Issue 19-22 https://doi.org/10.1080/00268970701618424	journal	October 2007
VPT2+K spectroscopic constants and matrix elements of the transformed vibrational Hamiltonian of a polyatomic molecule with resonances using Van Vleck perturbation theory Rosnik, Andreana M.; Polik, William F. Molecular Physics, Vol. 112, Issue 2 https://doi.org/10.1080/00268976.2013.808386	journal	June 2013
Vibrational Spectroscopy of Nitroalkane Chains Using Electron Autodetachment and Ar Predissociation Schneider, Holger; Vogelhuber, Kristen M.; Schinle, Florian The Journal of Physical Chemistry A, Vol. 112, Issue 33 https://doi.org/10.1021/jp800124s	journal	August 2008
The anharmonic force field of ethylene, C ₂ H ₄ , by means of accurate ab initio calculations Martin, Jan M. L.; Lee, Timothy J.; Taylor, Peter R. The Journal of Chemical Physics, Vol. 103, Issue 7 https://doi.org/10.1063/1.469681	journal	August 1995
Hartree–Fock orbital instability envelopes in highly correlated single-reference wave functions Crawford, T. Daniel; Stanton, John F.; Allen, Wesley D. The Journal of Chemical Physics, Vol. 107, Issue 24 https://doi.org/10.1063/1.474178	journal	December 1997
Triplet instability in doublet systems Szalay, Péter G.; Vázquez, Juana; Simmons, Chris The Journal of Chemical Physics, Vol. 121, Issue 16 https://doi.org/10.1063/1.1795153	journal	January 2004
Semiempirical hybrid density functional with perturbative second-order correlation Grimme, Stefan The Journal of Chemical Physics, Vol. 124, Issue 3 https://doi.org/10.1063/1.2148954	journal	January 2006
General Perturbative Approach for Spectroscopy, Thermodynamics, and Kinetics: Methodological Background and Benchmark Studies Bloino, Julien; Biczysko, Malgorzata; Barone, Vincenzo Journal of Chemical Theory and Computation, Vol. 8, Issue 3 https://doi.org/10.1021/ct200814m	journal	February 2012
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
A nonorthogonal CI treatment of symmetry breaking in sigma formyloxyl radical Ayala, Philippe Y.; Schlegel, H. Bernhard The Journal of Chemical Physics, Vol. 108, Issue 18 https://doi.org/10.1063/1.476190	journal	May 1998
The vibrational spectrum of H2O2+⋅ radical cation: An illustration of symmetry breaking Hrušák, Jan; Iwata, Suehiro The Journal of Chemical Physics, Vol. 106, Issue 12 https://doi.org/10.1063/1.473537	journal	March 1997
General Internal Motion of Molecules, Classical and Quantum‐Mechanical Hamiltonian Meyer, R.; Günthard, Hs. H. The Journal of Chemical Physics, Vol. 49, Issue 4 https://doi.org/10.1063/1.1670272	journal	August 1968
Periodic potential functions for pseudorotation and internal rotation Lewis, J. D.; Malloy, Thomas B.; Chao, Taina H. Journal of Molecular Structure, Vol. 12, Issue 3 https://doi.org/10.1016/0022-2860(72)87050-9	journal	June 1972
Ab Initio CBS-QCI Calculations of the Inversion Mode of Ammonia Rush, Daniel J.; Wiberg, Kenneth B. The Journal of Physical Chemistry A, Vol. 101, Issue 17 https://doi.org/10.1021/jp9624358	journal	April 1997

Cited By (1)

Infrared spectroscopy in superfluid helium droplets Verma, Deepak; Tanyag, Rico Mayro P.; O’Connell, Sean M. O. Advances in Physics: X, Vol. 4, Issue 1 https://doi.org/10.1080/23746149.2018.1553569	journal	December 2018

Similar Records

Photoelectron spectroscopy of isomeric C/sub 4/H/sub 7/ radicals: implications for the thermochemistry and structures of the radicals and their corresponding carbonium ions

Journal Article · Wed Nov 28 00:00:00 EST 1984 · J. Am. Chem. Soc.; (United States) · OSTI ID:1409066

Schultz, J C; Houle, F A; Beauchamp, J L

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and C Script-Small-L {sub 2} in solid para-hydrogen

Journal Article · Tue Aug 28 00:00:00 EDT 2012 · Journal of Chemical Physics · OSTI ID:1409066

Bahou, Mohammed; Wu, Jen-Yu; Tanaka, Keiichi; +1 more

Theoretical Prediction of the Ionization Energies of the C₄H₇ Radicals: 1-Methylallyl, 2-Methylallyl, Cyclopropylmethyl, and Cyclobutyl Radicals.

Journal Article · Mon Oct 15 00:00:00 EDT 2007 · Journal of Chemical Physics, 127:154302 1-12 · OSTI ID:1409066

Lau, Kai Chung; Zheng, Wenxu; Wong, Ning-Bew; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl, and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations

Citation Formats

References (61)

Cited By (1)

Similar Records

Related Subjects