Methyl radical

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Gas phase ion energetics data

Go To: Top, Vibrational and/or electronic energy levels, References, Notes

Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data evaluated as indicated in comments:
L - Sharon G. Lias

Data compiled as indicated in comments:
B - John E. Bartmess
LL - Sharon G. Lias and Joel F. Liebman
LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi
RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron

View reactions leading to CH3+ (ion structure unspecified)

Quantity Value Units Method Reference Comment
IE (evaluated)9.84 ± 0.01eVN/AN/AL
Quantity Value Units Method Reference Comment
Δf(+) ion261.8kcal/molN/AN/A 
Quantity Value Units Method Reference Comment
ΔfH(+) ion,0K262.6kcal/molN/AN/A 

Electron affinity determinations

EA (eV) Method Reference Comment
0.080 ± 0.030LPESEllison, Engelking, et al., 1978B
<0.499990PDFeldman, Rackwitz, et al., 1977B
<0.6244 ± 0.0053D-EABohme, Lee-Ruff, et al., 1972B
0.12983N/ACheck, Faust, et al., 2001FeBr3; ; ΔS(EA)=9.3; B
1.12747SIPage, 1972The Magnetron method, lacking mass analysis, is not considered reliable.; B
1.0 ± 1.1SIPage and Goode, 1969The Magnetron method, lacking mass analysis, is not considered reliable.; B
1.07543SIGaines and Page, 1968The Magnetron method, lacking mass analysis, is not considered reliable.; B

Ionization energy determinations

IE (eV) Method Reference Comment
9.843 ± 0.002EVALBerkowitz, Ellison, et al., 1994LL
9.84DERNagano, Murthy, et al., 1993LL
9.84 ± 0.02PEHoule and Beauchamp, 1979LLK
9.84 ± 0.05EIReeher, Flesch, et al., 1976LLK
9.6 ± 0.3EIKaposi, Riedel, et al., 1975LLK
9.837 ± 0.005PEGolob, Jonathan, et al., 1973LLK
9.86 ± 0.04PEPotts, Glenn, et al., 1972LLK
9.81 ± 0.02PEJonathan, 1972LLK
9.84 ± 0.03EILossing and Semeluk, 1970RDSH
9.87 ± 0.05EIWilliams and Hamill, 1968RDSH
9.83 ± 0.01PIChupka and Lifshitz, 1968RDSH
9.82 ± 0.04PIElder, Giese, et al., 1962RDSH
9.842 ± 0.002SHerzberg and Shoosmith, 1956RDSH
9.840 ± 0.005PEDyke, Jonathan, et al., 1976Vertical value; LLK
9.82 ± 0.02PEKoenig, Balle, et al., 1975Vertical value; LLK
9.86 ± 0.04PEPotts, Glenn, et al., 1972, 2Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
CH+15.58 ± 0.30H2EIWaldron, 1956RDSH
CH2+15.09 ± 0.03HPIChupka and Lifshitz, 1968RDSH

Cation De-protonation reactions

CH2- + Hydrogen cation = Methyl cation

By formula: CH2- + H+ = CH3+

Quantity Value Units Method Reference Comment
Δr409.11 ± 0.41kcal/molD-EALeopold, Murray, et al., 1985gas phase; Singlet-triplet splitting of CH2 = 9.0 kcal; B
Quantity Value Units Method Reference Comment
Δr401.42 ± 0.48kcal/molH-TSLeopold, Murray, et al., 1985gas phase; Singlet-triplet splitting of CH2 = 9.0 kcal; B

Vibrational and/or electronic energy levels

Go To: Top, Gas phase ion energetics data, References, Notes

Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data compiled by: Marilyn E. Jacox

State:   4f 2E'?


 Energy 
 (cm-1
 Med.   Transition   λmin 
 (nm) 
 λmax 
 (nm) 
 References

To = 72508 gas Hudgens, DiGiuseppe, et al., 1983

State:   4p 2A2


 Energy 
 (cm-1
 Med.   Transition   λmin 
 (nm) 
 λmax 
 (nm) 
 References

To = 69853.44 ± 0.13 gas Black and Powis, 1988

State:   3d 2A1'


 Energy 
 (cm-1
 Med.   Transition   λmin 
 (nm) 
 λmax 
 (nm) 
 References

To = 66805 gas 3d2A1'-X 147 150 Herzberg and Shoosmith, 1956
Herzberg, 1961
Tx 3d2A1'-X 150 151 Milligan and Jacox, 1967

State:   3d 2E


 Energy 
 (cm-1
 Med.   Transition   λmin 
 (nm) 
 λmax 
 (nm) 
 References

To = 66536 gas 3d2E''-X 144 150 Herzberg and Shoosmith, 1956
Herzberg, 1961
DiGiuseppe, Hudgens, et al., 1982


Vib. 
sym. 
 No.   Approximate 
 type of mode 
 cm-1   Med.   Method   References

a2 2 OPLA 1372 H gas AB MPI Herzberg, 1961
DiGiuseppe, Hudgens, et al., 1982

State:   3p 2A2


 Energy 
 (cm-1
 Med.   Transition   λmin 
 (nm) 
 λmax 
 (nm) 
 References

To = 59972 gas Hudgens, DiGiuseppe, et al., 1983
Heinze, Heberle, et al., 1994


Vib. 
sym. 
 No.   Approximate 
 type of mode 
 cm-1   Med.   Method   References

a1' 1 CH stretch 2931 gas MPI Hudgens, DiGiuseppe, et al., 1983
Zhang, Zhang, et al., 2005
a2 2 OPLA 1323 gas MPI Hudgens, DiGiuseppe, et al., 1983
Zhang, Zhang, et al., 2005
e' 3 CH stretch 3087 gas MPI Zhang, Zhang, et al., 2005
Fu, Hu, et al., 2005
4 Deformation 1428 T gas MPI Zhang, Zhang, et al., 2005

State:   3s 2A1'


 Energy 
 (cm-1
 Med.   Transition   λmin 
 (nm) 
 λmax 
 (nm) 
 References

To = 46239 gas 3s2A1'-X 216 Herzberg and Shoosmith, 1956
Herzberg, 1961
Callear and Metcalfe, 1976
Westre, Gansberg, et al., 1992
Settersten, Farrow, et al., 2003


Vib. 
sym. 
 No.   Approximate 
 type of mode 
 cm-1   Med.   Method   References

a1' 1 CH stretch 2040 T gas Ra Westre, Gansberg, et al., 1992

State:   X


Vib. 
sym. 
 No.   Approximate 
 type of mode 
 cm-1   Med.   Method   References

a1' 1 CH stretch 3004.43 ± 0.02 gas CARS Ra Holt, McCurdy, et al., 1984
Kelly and Westre, 1988
Triggs, Zahedi, et al., 1992
Zahedi, Harrison, et al., 1994
Hadrich, Hefter, et al., 1996
a2 2 OPLA 606.453 gas IR DL Tan, Winer, et al., 1972
Yamada, Hirota, et al., 1981
Wormhoudt and McCurdy, 1989
Stancu, Ropcke, et al., 2005
2 OPLA 617 vs Ne IR Snelson, 1970
2 OPLA 603 Ar IR Milligan and Jacox, 1967
Jacox, 1977
2 OPLA 624.0 p-H2 IR Lee and Lee, 2011
2 OPLA 611 N2 IR Milligan and Jacox, 1967
e' 3 CH stretch 3160.821 gas LD CC Amano, Bernath, et al., 1982
Tanarro, Sanz, et al., 1994
Tanarro, Sanz, et al., 1994, 2
Bethardy and Macdonald, 1995
Davis, Anderson, et al., 1997
3 CH stretch 3160.821 gas CR IR Scherer, Aniolek, et al., 1997
Kawaguchi, 2001
3 CH stretch 3162 w m Ne IR Snelson, 1970
3 CH stretch 3150 Ar IR Pacansky and Bargon, 1975
3 CH stretch 3171.4 H2 IR Momose, Miki, et al., 1995
Tam, Macler, et al., 1997
Hoshina, Fushitani, et al., 2011
3 CH stretch 3170.6 H2 IR Momose, Miki, et al., 1995
Tam, Macler, et al., 1997
Hoshina, Fushitani, et al., 2011
4 Deformation 1396 w Ne IR Snelson, 1970
4 Deformation 1398 Ar IR Jacox, 1977
4 Deformation 1402.7 H2 IR Momose, Miki, et al., 1995
Tam, Macler, et al., 1997
Hoshina, Fushitani, et al., 2011
4 Deformation 1401.6 H2 IR Momose, Miki, et al., 1995
Tam, Macler, et al., 1997
Hoshina, Fushitani, et al., 2011

Additional references: Jacox, 1994, page 125; Jacox, 1998, page 214; Jacox, 2003, page 156; Frye, Sears, et al., 1988; Parker, Wang, et al., 1989; Sears, Frye, et al., 1989; Westre and Kelly, 1989; Miller, Burton, et al., 1989; Fawzy, Sears, et al., 1990; Rudolph, Hall, et al., 1996

Notes

wWeak
mMedium
vsVery strong
H(1/2)(2ν)
TTentative assignment or approximate value
oEnergy separation between the v = 0 levels of the excited and electronic ground states.
xEnergy separation between the band maximum of the excited electronic state and the v = 0 level of the ground state.

References

Go To: Top, Gas phase ion energetics data, Vibrational and/or electronic energy levels, Notes

Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Ellison, Engelking, et al., 1978
Ellison, G.B.; Engelking, P.C.; Lineberger, W.C., An experimental determination of the geometry and electron affinity of CH3, J. Am. Chem. Soc., 1978, 100, 2556. [all data]

Feldman, Rackwitz, et al., 1977
Feldman, D.; Rackwitz, R.; Kaiser, H.J.; Heincke, E., Photodetachment bei einigen neagtiven molekulionen: P2-, As2-, CH2-, CH3-, S3-, Z. Naturforsch. A:, 1977, 32, 600. [all data]

Bohme, Lee-Ruff, et al., 1972
Bohme, D.K.; Lee-Ruff, E.; Young, L.B., Acidity order of selected bronsted acids in the gas phase at 300K, J. Am. Chem. Soc., 1972, 94, 5153. [all data]

Check, Faust, et al., 2001
Check, C.E.; Faust, T.O.; Bailey, J.M.; Wright, B.J.; Gilbert, T.M.; Sunderlin, L.S., Addition of Polarization and Diffuse Functions to the LANL2DZ Basis Set for P-Block Elements, J. Phys. Chem. A,, 2001, 105, 34, 8111, https://doi.org/10.1021/jp011945l . [all data]

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Page, F.M., Experimental determination of the electron affinities of inorganic radicals, Adv. Chem. Ser., 1972, 36, 68. [all data]

Page and Goode, 1969
Page, F.M.; Goode, G.C., Negative Ions and the Magnetron., Wiley, NY, 1969. [all data]

Gaines and Page, 1968
Gaines, A.F.; Page, F.M., The Stabilities of Negative Ions.I. The Methyl-, Diphenylmethyl, and Triphenylmethyl Negative Ions, Int. J. Mass Spectrom. Ion Phys., 1968, 1, 4-5, 315, https://doi.org/10.1016/0020-7381(68)85008-9 . [all data]

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Nagano, Y.; Murthy, S.; Beauchamp, J.L., Thermochemical properties and gas-phase ion chemistry of phenylsilane investigated by FT-ICR spectrometry. Identification of parent- and fragment-ion structural isomers by their specific reactivities, J. Am. Chem. Soc., 1993, 115, 10805. [all data]

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Houle, F.A.; Beauchamp, J.L., Photoelectron spectroscopy of methyl, ethyl, isopropyl, and tert-butyl radicals. Implications for the thermochemistry and structures of the radicals and their corresponding carbonium ions, J. Am. Chem. Soc., 1979, 101, 4067. [all data]

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Kaposi, Riedel, et al., 1975
Kaposi, O.; Riedel, M.; Sanchez, G.R., Mass-spectrometric study of electron-impact and heterogeneous pyrolytic decomposition of methyl bromide, Acta Chim. Acad. Sci. Hung., 1975, 85, 361. [all data]

Golob, Jonathan, et al., 1973
Golob, L.; Jonathan, N.; Morris, A.; Okuda, M.; Ross, K.J., The first ionization potential of the methyl radical as determined by photoelectron spectroscopy, J. Electron Spectrosc. Relat. Phenom., 1973, 1, 506. [all data]

Potts, Glenn, et al., 1972
Potts, A.W.; Glenn, K.G.; Price, W.C., General discussion, Faraday Discuss. Chem. Soc., 1972, 54, 64. [all data]

Jonathan, 1972
Jonathan, N., General discussion, Faraday Discuss. Chem. Soc., 1972, 54, 64. [all data]

Lossing and Semeluk, 1970
Lossing, F.P.; Semeluk, G.P., Free radicals by mass spectrometry. XLII.Ionization potentials and ionic heats of formation for C1-C4 alkyl radicals, Can. J. Chem., 1970, 48, 955. [all data]

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Williams, J.M.; Hamill, W.H., Ionization potentials of molecules and free radicals and appearance potentials by electron impact in the mass spectrometer, J. Chem. Phys., 1968, 49, 4467. [all data]

Chupka and Lifshitz, 1968
Chupka, W.A.; Lifshitz, C., Photoionization of CH3+; heat of formation of CH2, J. Chem. Phys., 1968, 48, 1109. [all data]

Elder, Giese, et al., 1962
Elder, F.A.; Giese, C.; Steiner, B.; Inghram, M., Photo-ionization of alkyl free radicals, J. Chem. Phys., 1962, 36, 3292. [all data]

Herzberg and Shoosmith, 1956
Herzberg, G.; Shoosmith, J., Absorption spectrum of free CH3 and CD3 radicals, Can. J. Phys., 1956, 34, 523. [all data]

Dyke, Jonathan, et al., 1976
Dyke, J.; Jonathan, N.; Lee, E.; Morris, A., Vacuum ultraviolet photoelectron spectroscopy of transient species, J. Chem. Soc. Faraday Trans. 2, 1976, 72, 1385. [all data]

Koenig, Balle, et al., 1975
Koenig, T.; Balle, T.; Snell, W., Helium(I) photoelectron spectra of organic radicals, J. Am. Chem. Soc., 1975, 97, 662. [all data]

Potts, Glenn, et al., 1972, 2
Potts, A.W.; Glenn, K.G.; Price, W.C., General discussion, Faraday Discuss. Chem. Soc., 1972, 54, 65. [all data]

Waldron, 1956
Waldron, J.D., The ionization and dissociation of methyl radicals on electron impact, Metropolitan Vickers Gaz., 1956, 27, 66. [all data]

Leopold, Murray, et al., 1985
Leopold, D.G.; Murray, K.K.; Miller, A.E.S.; Lineberger, W.C., Methylene: A study of the X3B1 and the 1A1 states by photoelectron spectroscopy of CH2- and CD2-, J. Chem. Phys., 1985, 83, 4849. [all data]

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Hudgens, J.W.; DiGiuseppe, T.G.; Lin, M.C., Two photon resonance enhanced multiphoton ionization spectroscopy and state assignments of the methyl radical, J. Chem. Phys., 1983, 79, 2, 571, https://doi.org/10.1063/1.445857 . [all data]

Black and Powis, 1988
Black, J.F.; Powis, I., Rotational structure and predissociation dynamics of the methyl 4pz(v=0) Rydberg state investigated by resonance enhanced multiphoton ionization spectroscopy, J. Chem. Phys., 1988, 89, 7, 3986, https://doi.org/10.1063/1.454832 . [all data]

Herzberg, 1961
Herzberg, G., The Bakerian Lecture. The Spectra and Structures of Free Methyl and Free Methylene, Proc. Roy. Soc. (London) A262, 1961, 262, 1310, 291, https://doi.org/10.1098/rspa.1961.0120 . [all data]

Milligan and Jacox, 1967
Milligan, D.E.; Jacox, M.E., Infrared and Ultraviolet Spectroscopic Study of the Products of the Vacuum-Ultraviolet Photolysis of Methane in Ar and N2 Matrices. The Infrared Spectrum of the Free Radical CH3, J. Chem. Phys., 1967, 47, 12, 5146, https://doi.org/10.1063/1.1701772 . [all data]

DiGiuseppe, Hudgens, et al., 1982
DiGiuseppe, T.G.; Hudgens, J.W.; Lin, M.C., Multiphoton ionization of methyl radicals in the gas phase, J. Phys. Chem., 1982, 86, 1, 36, https://doi.org/10.1021/j100390a008 . [all data]

Heinze, Heberle, et al., 1994
Heinze, J.; Heberle, N.; Kohse-Hoinghaus, K., The CH3 3pz2A2´´ ← X 2A2´´ 000 band at temperatures up to 1700 K investigated by REMPI spectroscopy, Chem. Phys. Lett., 1994, 223, 4, 305, https://doi.org/10.1016/0009-2614(94)00469-2 . [all data]

Zhang, Zhang, et al., 2005
Zhang, B.; Zhang, J.; Liu, K., Imaging the "missing" bands in the resonance-enhanced multiphoton ionization detection of methyl radical, J. Chem. Phys., 2005, 122, 10, 104310, https://doi.org/10.1063/1.1859277 . [all data]

Fu, Hu, et al., 2005
Fu, H.B.; Hu, Y.J.; Bernstein, E.R., IR/UV double resonant spectroscopy of the methyl radical: Determination of ν[sub 3] in the 3p[sub z] Rydberg state, J. Chem. Phys., 2005, 123, 23, 234307, https://doi.org/10.1063/1.2135772 . [all data]

Callear and Metcalfe, 1976
Callear, A.B.; Metcalfe, M.P., Oscillator strengths of the bands of the B2 A´1---X2 A´´2 system of CD3 and a spectroscopic measurement of the recombination rate comparison with CH3, Chem. Phys., 1976, 14, 2, 275, https://doi.org/10.1016/0301-0104(76)80045-6 . [all data]

Westre, Gansberg, et al., 1992
Westre, S.G.; Gansberg, T.E.; Kelly, P.B.; Ziegler, L.D., Structure and dynamics of higher vibronic levels in the methyl radical Rydberg 3s state, J. Phys. Chem., 1992, 96, 9, 3610, https://doi.org/10.1021/j100188a012 . [all data]

Settersten, Farrow, et al., 2003
Settersten, T.B.; Farrow, R.L.; Gray, J.A., Coherent infrared--ultraviolet double-resonance spectroscopy of CH3, Chem. Phys. Lett., 2003, 370, 1-2, 204, https://doi.org/10.1016/S0009-2614(03)00062-9 . [all data]

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Holt, P.L.; McCurdy, K.E.; Weisman, R.B.; Adams, J.S.; Engel, P.S., Transient CARS spectroscopy of the ν1 band of methyl radical, J. Chem. Phys., 1984, 81, 7, 3349, https://doi.org/10.1063/1.448000 . [all data]

Kelly and Westre, 1988
Kelly, P.B.; Westre, S.G., Resonance Raman spectroscopy of the methyl radical, Chem. Phys. Lett., 1988, 151, 3, 253, https://doi.org/10.1016/0009-2614(88)85284-9 . [all data]

Triggs, Zahedi, et al., 1992
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Zahedi, M.; Harrison, J.A.; Nibler, J.W., 266 nm CH3I photodissociation: CH3 spectra and population distributions by coherent Raman spectroscopy, J. Chem. Phys., 1994, 100, 6, 4043, https://doi.org/10.1063/1.466342 . [all data]

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Hadrich, S.; Hefter, S.; Pfelzer, B.; Doerk, T.; Jauernik, P.; Uhlenbusch, J., Determination of the absolute Raman cross section of methyl, Chem. Phys. Lett., 1996, 256, 1-2, 83, https://doi.org/10.1016/0009-2614(96)00411-3 . [all data]

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Tan, L.Y.; Winer, A.M.; Pimentel, G.C., Infrared Spectrum of Gaseous Methyl Radical by Rapid Scan Spectroscopy, J. Chem. Phys., 1972, 57, 9, 4028, https://doi.org/10.1063/1.1678876 . [all data]

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Wormhoudt, J.; McCurdy, K.E., A measurement of the strength of the ν2 band of CH3, Chem. Phys. Lett., 1989, 156, 1, 47, https://doi.org/10.1016/0009-2614(89)87078-2 . [all data]

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Snelson, A., Infrared matrix isolation spectrum of the methyl radical produced by pyrolysis of methyl iodide and dimethyl mercury, J. Phys. Chem., 1970, 74, 3, 537, https://doi.org/10.1021/j100698a011 . [all data]

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Lee, Y.-F.; Lee, Y.-P., Infrared absorption of CH3SO2 observed upon irradiation of a p-H2 matrix containing CH3I and SO2, J. Chem. Phys., 2011, 1334, 12, 124314, https://doi.org/10.1063/1.3567117 . [all data]

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Davis, S.; Anderson, D.T.; Duxbury, G.; Nesbitt, D.J., Jet-cooled molecular radicals in slit supersonic discharges: Sub-Doppler infrared studies of methyl radical, J. Chem. Phys., 1997, 107, 15, 5661, https://doi.org/10.1063/1.474259 . [all data]

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Scherer, J.J.; Aniolek, K.W.; Cernansky, N.P.; Rakestraw, D.J., Determination of methyl radical concentrations in a methane/air flame by infrared cavity ringdown laser absorption spectroscopy, J. Chem. Phys., 1997, 107, 16, 6196, https://doi.org/10.1063/1.474284 . [all data]

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Pacansky, J.; Bargon, J., Low temperature photochemical studies on acetyl benzoyl peroxide. Observation of methyl and phenyl radicals by matrix isolation infrared spectroscopy, J. Am. Chem. Soc., 1975, 97, 23, 6896, https://doi.org/10.1021/ja00856a066 . [all data]

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Hoshina, H.; Fushitani, M.; Momose, T., Infrared spectroscopy of rovibrational transitions of methyl radicals (CH3, CD3) in solid parahydrogen, J. Mol. Spectrosc., 2011, 268, 1-2, 164, https://doi.org/10.1016/j.jms.2011.04.014 . [all data]

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Frye, J.M.; Sears, T.J.; Leitner, D., Diode laser spectroscopy of the ν2 band of CD3, J. Chem. Phys., 1988, 88, 9, 5300, https://doi.org/10.1063/1.454588 . [all data]

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Parker, D.H.; Wang, Z.W.; Janssen, M.H.M.; Chandler, D.W., Laser ionization spectroscopy of CD3 via the 3pz 2A'2 Rydberg state, J. Chem. Phys., 1989, 90, 1, 60, https://doi.org/10.1063/1.456466 . [all data]

Sears, Frye, et al., 1989
Sears, T.J.; Frye, J.M.; Spirko, V.; Kraemer, W.P., Extended measurements of the ν2 band of CD3 and the determination of the vibrational potential function for methyl, J. Chem. Phys., 1989, 90, 4, 2125, https://doi.org/10.1063/1.456006 . [all data]

Westre and Kelly, 1989
Westre, S.G.; Kelly, P.B., Examination of CD3 vibrational structure by resonance Raman spectroscopy, J. Chem. Phys., 1989, 90, 12, 6977, https://doi.org/10.1063/1.456273 . [all data]

Miller, Burton, et al., 1989
Miller, J.T.; Burton, K.A.; Weisman, R.B.; Wu, W.-X.; Engel, P.S., Cars spectroscopy of gas phase CD3, Chem. Phys. Lett., 1989, 158, 3-4, 179, https://doi.org/10.1016/0009-2614(89)87317-8 . [all data]

Fawzy, Sears, et al., 1990
Fawzy, W.M.; Sears, T.J.; Davies, P.B., Infrared diode laser spectroscopy of the ν3 fundamental of the CD3 radical, J. Chem. Phys., 1990, 92, 12, 7021, https://doi.org/10.1063/1.458242 . [all data]

Rudolph, Hall, et al., 1996
Rudolph, R.N.; Hall, G.E.; Sears, T.J., Measurement of the ν3 fundamental transition moment and vibrational relaxation rates of the CD3 radical, J. Chem. Phys., 1996, 105, 18, 7889, https://doi.org/10.1063/1.472704 . [all data]


Notes

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