Difluoromethyl radical

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Reaction thermochemistry data

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

Data compiled by: José A. Martinho Simões

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Individual Reactions

C6HF2MnO5 (g) = C5MnO5 (g) + Difluoromethyl radical (g)

By formula: C6HF2MnO5 (g) = C5MnO5 (g) + CHF2 (g)

Quantity Value Units Method Reference Comment
Δr34.4 ± 3.6kcal/molPIMSMartinho Simões and Beauchamp, 1990The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 213.3 ± 1.1 kcal/mol, using Mn(CO)5(CHF2) as the neutral precursor, together with the adiabatic ionization energy of Mn(CO)5 radical, 179. ± 3.3 kcal/mol Martinho Simões and Beauchamp, 1990

Gas phase ion energetics data

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

Data compiled as indicated in comments:
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
B - John E. Bartmess

View reactions leading to CHF2+ (ion structure unspecified)

Electron affinity determinations

EA (eV) Method Reference Comment
1.21 ± 0.16D-EAGraul and Squires, 1990G2 calculations( Lee, Dyke, et al., 1998) predict ΔHacid = 399 kcal/mol; B

Ionization energy determinations

IE (eV) Method Reference Comment
10.5EIGoto, Nakamura, et al., 1994LL
8.78DERLias, Bartmess, et al., 1988LL
8.74PEAue and Bowers, 1979LLK
9.45DERSyrvatka, Gil'burd, et al., 1973LLK
≤8.90EILossing, 1972LLK
9.45EILossing, Kebarle, et al., 1959RDSH

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
CF+20.5H+FEIGoto, Nakamura, et al., 1994LL
CF+14.6HFEIGoto, Nakamura, et al., 1994LL
CF2+17.2HEIGoto, Nakamura, et al., 1994LL
CH+28.02FEIGoto, Nakamura, et al., 1994LL
CH+27.2F2EIGoto, Nakamura, et al., 1994LL
CHF+14.3FEIGoto, Nakamura, et al., 1994LL

Vibrational and/or electronic energy levels

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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:   F 3p


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

To = 49312 ± 10 gas Dearden, Hudgens, et al., 1992


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

a1 2 CF stretch 1365 ± 8 gas MPI Dearden, Hudgens, et al., 1992
3 CF2 scissors 660 ± 20 gas MPI Dearden, Hudgens, et al., 1992
b1 4 OPLA 1022 ± 1 gas MPI Dearden, Hudgens, et al., 1992

State:   X


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

a' 2 CF s-stretch 1164 s Ar IR Carver and Andrews, 1969
Jacox, 1980
3 Umbrella 949 ± 10 gas MPI Dearden, Hudgens, et al., 1992
a 5 HCF deform. 1317 m Ar IR Carver and Andrews, 1969
Jacox, 1980
6 CF a-stretch 1173 vs Ar IR Carver and Andrews, 1969
Jacox, 1980

Additional references: Jacox, 1994, page 176; Jacox, 2003, page 199; Fessenden and Schuler, 1965

Notes

mMedium
sStrong
vsVery strong
oEnergy separation between the v = 0 levels of the excited and electronic ground states.

References

Go To: Top, Reaction thermochemistry data, 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.

Martinho Simões and Beauchamp, 1990
Martinho Simões, J.A.; Beauchamp, J.L., Chem. Rev., 1990, 90, 629. [all data]

Graul and Squires, 1990
Graul, S.T.; Squires, R.R., Gas-Phase Acidities Derived from Threshold Energies for Activated Reactions, J. Am. Chem. Soc., 1990, 112, 7, 2517, https://doi.org/10.1021/ja00163a007 . [all data]

Lee, Dyke, et al., 1998
Lee, E.P.F.; Dyke, J.M.; Mayhew, C.A., Study of the OH-+CH2F2 reaction by selected ion flow tube experiments and ab initio calculations, J. Phys. Chem. A, 1998, 102, 43, 8349-8354, https://doi.org/10.1021/jp982224y . [all data]

Goto, Nakamura, et al., 1994
Goto, M.; Nakamura, K.; Toyoda, H.; Sugai, H., Cross section measurements for electron-impact dissociation of CHF3 into neutral and ionic fragments, Jpn. J. Appl. Phys. Part 1, 1994, 33, 3602. [all data]

Lias, Bartmess, et al., 1988
Lias, S.G.; Bartmess, J.E.; Liebman, J.F.; Holmes, J.L.; Levin, R.D.; Mallard, W.G., Gas-phase ion and neutral thermochemistry, J. Phys. Chem. Ref. Data, Suppl. 1, 1988, 17, 1-861. [all data]

Aue and Bowers, 1979
Aue, D.H.; Bowers, M.T., Chapter 9. Stabilities of positive ions from equilibrium gas phase basicity measurements in Ions Chemistry,, ed. M.T. Bowers, 1979. [all data]

Syrvatka, Gil'burd, et al., 1973
Syrvatka, B.G.; Gil'burd, M.M.; Bel'ferman, A.L., Ion-dissociative processes of some halogen containing butadienes and particles structure, Zh. Org. Khim., 1973, 9, 1117. [all data]

Lossing, 1972
Lossing, F.P., Free radicals by mass spectrometry. XLIV. Ionization potentials bond dissociation energies for chloro-and fluoromethyl radicals, Bull. Soc. Chim. Belg., 1972, 81, 125. [all data]

Lossing, Kebarle, et al., 1959
Lossing, F.P.; Kebarle, P.; DeSousa, J.B., Ionization potentials of alkyl and halogenated alkyl free radicals, 1959. [all data]

Dearden, Hudgens, et al., 1992
Dearden, D.V.; Hudgens, J.W.; Johnson, R.D., III; Tsai, B.P.; Kafafi, S.A., Spectroscopic and ab initio studies of difluoromethyl radicals and cations, J. Phys. Chem., 1992, 96, 2, 585, https://doi.org/10.1021/j100181a017 . [all data]

Carver and Andrews, 1969
Carver, T.G.; Andrews, L., Infrared Spectrum of the Difluoromethyl Radical in Solid Argon, J. Chem. Phys., 1969, 50, 12, 5100, https://doi.org/10.1063/1.1671024 . [all data]

Jacox, 1980
Jacox, M.E., Infrared spectroscopic study of the reaction of H atoms with CF2 in argon and nitrogen matrices, J. Mol. Spectrosc., 1980, 81, 2, 349, https://doi.org/10.1016/0022-2852(80)90198-8 . [all data]

Jacox, 1994
Jacox, M.E., Vibrational and electronic energy levels of polyatomic transient molecules, American Chemical Society, Washington, DC, 1994, 464. [all data]

Jacox, 2003
Jacox, M.E., Vibrational and electronic energy levels of polyatomic transient molecules: supplement B, J. Phys. Chem. Ref. Data, 2003, 32, 1, 1-441, https://doi.org/10.1063/1.1497629 . [all data]

Fessenden and Schuler, 1965
Fessenden, R.W.; Schuler, R.H., ESR Spectra and Structure of the Fluorinated Methyl Radicals, J. Chem. Phys., 1965, 43, 8, 2704, https://doi.org/10.1063/1.1697199 . [all data]


Notes

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