Trifluoromethyl 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 compiled as indicated in comments:
B - John E. Bartmess
LL - Sharon G. Lias and Joel F. Liebman
LBLHLM - Sharon G. Lias, John E. Bartmess, Joel F. Liebman, John L. Holmes, Rhoda D. Levin, and W. Gary Mallard
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 CF3+ (ion structure unspecified)

Electron affinity determinations

EA (eV) Method Reference Comment
1.820 ± 0.050LPESDeyerl, Alconcel, et al., 2001Adiabatic EA, from vibrational structure of spectrum; B
1.90 ± 0.30NBAEDispert and Lacmann, 1978From CF4; B
2.820 ± 0.010PDRichardson, Stephenson, et al., 1975Stated electron affinity is the Vertical Detachment Energy; B
1.87003EIAEWang, Margrave, et al., 1973From CF4; B
1.80 ± 0.20EIAEThynne and MacNeil, 1970From CF3OF; B
2.00008EIAELifshitz and Grajower, 1969From C3F8. G3MP2B3 calculations indicate an EA of ca. 2.0 eV.; B
2.80 ± 0.20N/ASpyrou, Sauers, et al., 1983From CF4, relative to F- appearance energy; B
2.19999EIAEFranklin, Wang, et al., 1974From CF4; B
2.20 ± 0.30EIAEHarland and Franklin, 1974From CF4; B
>2.40 ± 0.50EIAEHarland and Franklin, 1974From C2F6; B
>2.05 ± 0.20EIAEHarland and Franklin, 1974From C3F8.; B
3.15 ± 0.20EIAELifshitz and Grajower, 1972From CF4; B
2.50211EIAEHarland and Thynne, 1970From (CF3)2CO; B
2.70 ± 0.20EIAEMacNeil and Thynne, 1970From CF4; B
2.10 ± 0.30EIAEThynne and MacNeil, 1970, 2From C2F4; B
<2.60185EIAEMacNeil and Thynne, 1969From C2F6; B
3.24997EIAEBibby and Carter, 1963From C2F6; B
1.97 ± 0.23SIPage and Goode, 1969The Magnetron method, lacking mass analysis, is not considered reliable.; B

Ionization energy determinations

IE (eV) Method Reference Comment
8.76IMBTsuji, Aizawa, et al., 1995LL
10.6EIGoto, Nakamura, et al., 1994LL
8.5 ± 0.8EITarnovsky and Becker, 1993LL
8.60 ± 0.07ENDFischer and Armentrout, 1990LL
9.3 ± 0.2EIKime, Driscoll, et al., 1987LBLHLM
8.9DERLoguinov, Takhistov, et al., 1981LLK
9.14DERBerman, Beauchamp, et al., 1981LLK
9.17PEAue and Bowers, 1979LLK
9.5DERSyrvatka, Gil'burd, et al., 1973LLK
9.11DERWalter, Lifshitz, et al., 1969RDSH
9.8 ± 0.2EIEhlert, 1969RDSH
9.25 ± 0.04PILifshitz and Chupka, 1967RDSH

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
CF+22.22FEIGoto, Nakamura, et al., 1994LL
CF+21.4F2EIGoto, Nakamura, et al., 1994LL
CF+21.4 ± 0.42FEITarnovsky, Kurunczi, et al., 1993LL
CF2+18.9FEIGoto, Nakamura, et al., 1994LL
CF2+17.1 ± 0.4FEITarnovsky, Kurunczi, et al., 1993LL

Anion protonation reactions

CF3- + Hydrogen cation = Fluoroform

By formula: CF3- + H+ = CHF3

Quantity Value Units Method Reference Comment
Δr1582. ± 5.9kJ/molD-EADeyerl, Alconcel, et al., 2001gas phase; Adiabatic EA, from vibrational structure of spectrum; B
Δr1577. ± 8.8kJ/molG+TSBartmess, Scott, et al., 1979gas phase; Paulino and Squires, 1991 suggests that this acidity may be too weak by ca. 5 kcal/mol. However, G2 calcn(JEB) give ΔHacid=379.9, ΔGacid=372.0; value altered from reference due to change in acidity scale; B
Δr1573. ± 19.kJ/molCIDTGraul and Squires, 1990gas phase; B
Quantity Value Units Method Reference Comment
Δr1549. ± 6.3kJ/molH-TSDeyerl, Alconcel, et al., 2001gas phase; Adiabatic EA, from vibrational structure of spectrum; B
Δr1545. ± 8.4kJ/molIMREBartmess, Scott, et al., 1979gas phase; Paulino and Squires, 1991 suggests that this acidity may be too weak by ca. 5 kcal/mol. However, G2 calcn(JEB) give ΔHacid=379.9, ΔGacid=372.0; value altered from reference due to change in acidity scale; 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:   Ryd


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

gas 139 165 Basco and Hathorn, 1971
Duignan, Hudgens, et al., 1982


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

a2 2 OPLA 820 gas AB MPI Basco and Hathorn, 1971
Duignan, Hudgens, et al., 1982

State:   4s 2A1'


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

To = 51665 T gas 4s2A1'-X 180 300 Glanzer, Maier, et al., 1980
Suto and Washida, 1983
Suto and Washida, 1983, 2
Suto, Washida, et al., 1983
Washida, Suto, et al., 1983
Suto and Lee, 1983
Ohoyama, Kasai, et al., 1986
Creasey, Lambert, et al., 1990

State:   3p 2A2


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

To = 51600 T gas 3p-3s2A1' 450 750 Flamm, 1980
Suto and Washida, 1983
Suto, Washida, et al., 1983
Washida, Suto, et al., 1983
Creasey, Lambert, et al., 1990

State:   4s


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

a1' 1 Sym. stretch 804 T gas EM Suto and Washida, 1983, 2

State:   X


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

a1 1 CF stretch 1089 gas IR EM Carlson and Pimentel, 1966
Suto and Washida, 1983, 2
1 CF stretch 1089 gas CARS Bozlee and Nibler, 1986
1 CF stretch 1086 Ne IR Snelson, 1970
Forney, Jacox, et al., 1994
1 CF stretch 1087 s Ar IR Milligan, Jacox, et al., 1966
Milligan and Jacox, 1968
2 Umbrella 701 ± 3 gas IR EM Carlson and Pimentel, 1966
Suto and Washida, 1983, 2
2 Umbrella 701.4 Ne IR Snelson, 1970
Forney, Jacox, et al., 1994
2 Umbrella 703 m Ar IR Milligan, Jacox, et al., 1966
Milligan and Jacox, 1968
e 3 CF stretch 1260.16 gas IR DL Carlson and Pimentel, 1966
Yamada and Hirota, 1983
3 CF stretch 1253.8 Ne IR Snelson, 1970
Forney, Jacox, et al., 1994
3 CF stretch 1251 vs Ar IR Milligan, Jacox, et al., 1966
Milligan and Jacox, 1968
4 Deformation 508.7 Ne IR Snelson, 1970
Forney, Jacox, et al., 1994
4 Deformation 512 w Ar IR Milligan and Jacox, 1968

Additional references: Jacox, 1994, page 215; Jacox, 1998, page 261; Fessenden and Schuler, 1965; Endo, Yamada, et al., 1982; Quick, Tiee, et al., 1985; Dreyfus and Urbach, 1985; Hermann, 1990

Notes

wWeak
mMedium
sStrong
vsVery strong
TTentative assignment or approximate value
oEnergy separation between the v = 0 levels of the excited and electronic ground states.

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.

Deyerl, Alconcel, et al., 2001
Deyerl, H.J.; Alconcel, L.S.; Continetti, R.E., Photodetachment imaging studies of the electron affinity of CF3, J. Phys. Chem. A, 2001, 105, 3, 552-557, https://doi.org/10.1021/jp003137k . [all data]

Dispert and Lacmann, 1978
Dispert, H.; Lacmann, K., Negative ion formation in collisions between potassium and fluoro- and chloromethanes: Electron affinities and bond dissociation energies, Int. J. Mass Spectrom. Ion Phys., 1978, 28, 49. [all data]

Richardson, Stephenson, et al., 1975
Richardson, J.H.; Stephenson, L.M.; Brauman, J.I., Photodetachment of electrons from trifluoromethyl and trifluorosilyl ions the electron affinities of CF3 and SiF3, Chem. Phys. Lett., 1975, 30, 17. [all data]

Wang, Margrave, et al., 1973
Wang, J.L.-F.; Margrave, J.L.; Franklin, J.L., Interpretation of dissociative electron attachment processes for carbon and silicon tetrafluorides, J. Chem. Phys., 1973, 58, 5417. [all data]

Thynne and MacNeil, 1970
Thynne, J.C.J.; MacNeil, K.A.G., Ionisation and dissociation of carbonyl fluoride and trifluoromethyl hypofluorite by electron impact, Intern. J. Mass Spectrom. Ion Phys., 1970, 5, 95. [all data]

Lifshitz and Grajower, 1969
Lifshitz, C.; Grajower, R., Dissociative electron capture and dissociative ionization in perfluoropropane, Intern. J. Mass Spectrom. Ion Phys., 1969, 3, 211. [all data]

Spyrou, Sauers, et al., 1983
Spyrou, S.M.; Sauers, I.; Christophorou, L.G., Electron attachment to the perfluoroalkanes n-CnF2n+2 (n = 1-6) and i-C4F10, J. Chem. Phys., 1983, 78, 7200. [all data]

Franklin, Wang, et al., 1974
Franklin, J.L.; Wang, J.L.-F.; Bennett, S.L.; Harland, P.W.; Margrave, J.L., Studies of the energies of negative ions at high temperatures, Adv. Mass Spectrom., 1974, 6, 319. [all data]

Harland and Franklin, 1974
Harland, P.W.; Franklin, J.L., Partitioning of excess energy in dissociative resonance capture processes, J. Chem. Phys., 1974, 61, 1621. [all data]

Lifshitz and Grajower, 1972
Lifshitz, C.; Grajower, R., Dissociative electron capture and dissociative ionization in perfluorocyclobutane, Int. J. Mass Spectrom. Ion Phys., 1972, 10, 25. [all data]

Harland and Thynne, 1970
Harland, P.; Thynne, J.C.J., Positive and negative ion formation in hexafluoroacetone by electron impact, J. Phys. Chem., 1970, 74, 52. [all data]

MacNeil and Thynne, 1970
MacNeil, K.A.G.; Thynne, J.C.J., The Formation of Negative Ions by Electron Impact on Silicon Tetrafluoride and Carbon Tetrafluoride, Int. J. Mass Spectrom. Ion Phys., 1970, 3, 6, 455, https://doi.org/10.1016/0020-7381(70)80004-3 . [all data]

Thynne and MacNeil, 1970, 2
Thynne, J.C.J.; MacNeil, K.A.G., Ionisation of Tetrafluoroethylene by Electron Impact, Int. J. Mass Spectrom. Ion Phys., 1970, 5, 3-4, 329, https://doi.org/10.1016/0020-7381(70)80026-2 . [all data]

MacNeil and Thynne, 1969
MacNeil, K.A.G.; Thynne, J.C.J., Ionization and Dissociation of Hexafluoroethane, and of 1,1,1-Trifluoroethane and Fluoroform, by Electron Impact, Int. J. Mass Spectrom. Ion Phys., 1969, 2, 1, 1, https://doi.org/10.1016/0020-7381(69)80001-X . [all data]

Bibby and Carter, 1963
Bibby, M.M.; Carter, G., Ionization and dissociation in some fluorocarbon gases, J. Chem. Soc. Faraday Trans., 1963, 59, 2455. [all data]

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

Tsuji, Aizawa, et al., 1995
Tsuji, M.; Aizawa, M.; Nishimura, Y., Mass spectroscopic studies on ion-molecule reactions of CF3+ with benzene and toluene at near-thermal energy, Chem. Lett., 1995, 3, 211. [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]

Tarnovsky and Becker, 1993
Tarnovsky, V.; Becker, K., Absolute partial cross sections for the parent ionization of the CFx (x = 1-3) free radicals by electron impact, J. Chem. Phys., 1993, 98, 7868. [all data]

Fischer and Armentrout, 1990
Fischer, E.R.; Armentrout, P.B., The appearance energy of CF3+ from CF4: Ion/molecule reactions related to the thermochemistry of CF3+., Int. J. Mass Spectrom. Ion Processes, 1990, 101, 1. [all data]

Kime, Driscoll, et al., 1987
Kime, Y.J.; Driscoll, D.C.; Dowben, P.A., The stability of the carbon tetrahalide ions, J. Chem. Soc. Faraday Trans. 2, 1987, 83, 403. [all data]

Loguinov, Takhistov, et al., 1981
Loguinov, Y.; Takhistov, V.V.; Vatlina, L.P., Photoionization studies of substituted trimethylamines, Org. Mass Spectrom., 1981, 16, 239. [all data]

Berman, Beauchamp, et al., 1981
Berman, D.W.; Beauchamp, J.L.; Thorne, L.R., Ion cyclotron resonance and photoionization investigations of the thermochemistry and reactions of ions derived from CF3I, Int. J. Mass Spectrom. Ion Phys., 1981, 39, 47. [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]

Walter, Lifshitz, et al., 1969
Walter, T.A.; Lifshitz, C.; Chupka, W.A.; Berkowitz, J., Mass-spectrometric study of the photoionization of C2F4 and CF4, J. Chem. Phys., 1969, 51, 3531. [all data]

Ehlert, 1969
Ehlert, T.C., Bonding in C1 and C2 fluorides, J. Phys. Chem., 1969, 73, 949. [all data]

Lifshitz and Chupka, 1967
Lifshitz, C.; Chupka, W.A., Photoionization of the CF3 free radical, J. Chem. Phys., 1967, 47, 3439. [all data]

Tarnovsky, Kurunczi, et al., 1993
Tarnovsky, V.; Kurunczi, P.; Rogozhnikov, D.; Becker, K., Absolute cross sections for the dissociative electron impact ionization of the CFx (x=1-3) free radicals, Int. J. Mass Spectrom. Ion Processes, 1993, 128, 181. [all data]

Bartmess, Scott, et al., 1979
Bartmess, J.E.; Scott, J.A.; McIver, R.T., Jr., The gas phase acidity scale from methanol to phenol, J. Am. Chem. Soc., 1979, 101, 6047. [all data]

Paulino and Squires, 1991
Paulino, J.A.; Squires, R.R., Carbene Thermochemistry from Collision-Induced Dissociation Threshold Energy Measurements - The Heats of Formation of X1A1 CF2 and X1A1 CCl2, J. Am. Chem. Soc., 1991, 113, 15, 5573, https://doi.org/10.1021/ja00015a009 . [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]

Basco and Hathorn, 1971
Basco, N.; Hathorn, F.G.M., The electronic absorption spectrum of the trifluoromethyl radical, Chem. Phys. Lett., 1971, 8, 3, 291, https://doi.org/10.1016/0009-2614(71)85015-7 . [all data]

Duignan, Hudgens, et al., 1982
Duignan, M.T.; Hudgens, J.W.; Wyatt, J.R., Multiphoton ionization of the trifluoromethyl radical, J. Phys. Chem., 1982, 86, 21, 4156, https://doi.org/10.1021/j100218a013 . [all data]

Glanzer, Maier, et al., 1980
Glanzer, K.; Maier, M.; Troe, J., Shock-wave study of the high-temperature uv absorption and the recombination of trifluoromethyl radicals, J. Phys. Chem., 1980, 84, 13, 1681, https://doi.org/10.1021/j100450a004 . [all data]

Suto and Washida, 1983
Suto, M.; Washida, N., Emission spectra of CF3 radicals. I. UV and visible emission spectra of CF3 observed in the VUV photolysis and the metastable argon atom reaction of CF3H, J. Chem. Phys., 1983, 78, 3, 1007, https://doi.org/10.1063/1.444899 . [all data]

Suto and Washida, 1983, 2
Suto, M.; Washida, N., Emission spectra of CF3 radicals. II. Analysis of the UV emission spectrum of CF3 radicals, J. Chem. Phys., 1983, 78, 3, 1012, https://doi.org/10.1063/1.444900 . [all data]

Suto, Washida, et al., 1983
Suto, M.; Washida, N.; Akimoto, H.; Nakamura, M., Emission spectra of CF3 radicals. III. Spectra and quenching of CF3 emission bands produced in the VUV photolyses of CF3Cl and CF3Br, J. Chem. Phys., 1983, 78, 3, 1019, https://doi.org/10.1063/1.444901 . [all data]

Washida, Suto, et al., 1983
Washida, N.; Suto, M.; Nagase, S.; Nagashima, U.; Morokuma, K., Emission spectra of CF3 radicals. IV. Excitation spectra, quantum yields, and potential energy surfaces of the CF3 fluorescences, J. Chem. Phys., 1983, 78, 3, 1025, https://doi.org/10.1063/1.444902 . [all data]

Suto and Lee, 1983
Suto, M.; Lee, C., Emission spectra of CF3 radicals. V. Photodissociation of CF3H, CF3Cl, and CF3Br by vacuum ultraviolet, J. Chem. Phys., 1983, 79, 3, 1127, https://doi.org/10.1063/1.445914 . [all data]

Ohoyama, Kasai, et al., 1986
Ohoyama, H.; Kasai, T.; Ohashi, K.; Hirata, Y.; Kuwata, K., Chemiluminescence of CF3 in the visible region from the crossed beam reaction of Ar(3P2,0) with CF3H, Chem. Phys. Lett., 1986, 131, 1-2, 20, https://doi.org/10.1016/0009-2614(86)80510-3 . [all data]

Creasey, Lambert, et al., 1990
Creasey, J.C.; Lambert, I.R.; Tuckett, R.P.; Hopkirk, A., Vacuum UV spectroscopy and dynamics of CHF, Mol. Phys., 1990, 71, 6, 1355, https://doi.org/10.1080/00268979000102531 . [all data]

Flamm, 1980
Flamm, D.L., Mechanisms of radical production in radiofrequency discharges of CF3Cl, CF3Br, and certain other plasma etchants: Spectrum of a transient species, J. Appl. Phys., 1980, 51, 11, 5688, https://doi.org/10.1063/1.327567 . [all data]

Carlson and Pimentel, 1966
Carlson, G.A.; Pimentel, G.C., Infrared Detection of Gaseous Trifluoromethyl Radical, J. Chem. Phys., 1966, 44, 10, 4053, https://doi.org/10.1063/1.1726574 . [all data]

Bozlee and Nibler, 1986
Bozlee, B.J.; Nibler, J.W., Coherent anti-Stokes Raman spectra study of CF3 and NO photofragments of CF3NO, J. Chem. Phys., 1986, 84, 7, 3798, https://doi.org/10.1063/1.450090 . [all data]

Snelson, 1970
Snelson, A., High Temp. Sci., 1970, 2, 70. [all data]

Forney, Jacox, et al., 1994
Forney, D.; Jacox, M.E.; Irikura, K.K., Matrix isolation study of the interaction of excited neon atoms with CF4. Infrared spectra of CF+3 and CF-3, J. Chem. Phys., 1994, 101, 10, 8290, https://doi.org/10.1063/1.468094 . [all data]

Milligan, Jacox, et al., 1966
Milligan, D.E.; Jacox, M.E.; Comeford, J.J., Infrared Spectrum of the Free Radical CF3 Isolated in Inert Matrices, J. Chem. Phys., 1966, 44, 10, 4058, https://doi.org/10.1063/1.1726578 . [all data]

Milligan and Jacox, 1968
Milligan, D.E.; Jacox, M.E., Matrix-Isolation Study of the Reaction of Atomic and Molecular Fluorine with Carbon Atoms. The Infrared Spectra of Normal and 13C-Substituted CF2 and CF3, J. Chem. Phys., 1968, 48, 5, 2265, https://doi.org/10.1063/1.1669423 . [all data]

Yamada and Hirota, 1983
Yamada, C.; Hirota, E., Infrared diode laser spectroscopy of the CF3 ν3 band, J. Chem. Phys., 1983, 78, 4, 1703, https://doi.org/10.1063/1.444969 . [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, 1998
Jacox, M.E., Vibrational and electronic energy levels of polyatomic transient molecules: supplement A, J. Phys. Chem. Ref. Data, 1998, 27, 2, 115-393, https://doi.org/10.1063/1.556017 . [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]

Endo, Yamada, et al., 1982
Endo, Y.; Yamada, C.; Saito, S.; Hirota, E., The microwave spectrum of the trifluoromethyl radical, J. Chem. Phys., 1982, 77, 7, 3376, https://doi.org/10.1063/1.444279 . [all data]

Quick, Tiee, et al., 1985
Quick, C.R., Jr.; Tiee, J.J.; Preses, J.; Weston, R.E., Jr., Fluorescence lifetime and quenching rate measurements of the ultraviolet and visible emission bands of the CF3 radical, Chem. Phys. Lett., 1985, 114, 4, 371, https://doi.org/10.1016/0009-2614(85)85101-0 . [all data]

Dreyfus and Urbach, 1985
Dreyfus, R.W.; Urbach, L., Fluorescence of CF3* radicals, Chem. Phys. Lett., 1985, 114, 4, 376, https://doi.org/10.1016/0009-2614(85)85102-2 . [all data]

Hermann, 1990
Hermann, R., Radiat. Phys. Chem., 1990, 36, 227. [all data]


Notes

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