Methylene, difluoro-

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Gas phase thermochemistry data

Go To: Top, Reaction thermochemistry data, 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:
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein

Quantity Value Units Method Reference Comment
Δfgas-43.499kcal/molReviewChase, 1998Data last reviewed in June, 1970
Δfgas-41.1 ± 2.0kcal/molEqkEhlert, 1969ALS
Quantity Value Units Method Reference Comment
gas,1 bar57.560cal/mol*KReviewChase, 1998Data last reviewed in June, 1970

Gas Phase Heat Capacity (Shomate Equation)

Cp° = A + B*t + C*t2 + D*t3 + E/t2
H° − H°298.15= A*t + B*t2/2 + C*t3/3 + D*t4/4 − E/t + F − H
S° = A*ln(t) + B*t + C*t2/2 + D*t3/3 − E/(2*t2) + G
    Cp = heat capacity (cal/mol*K)
    H° = standard enthalpy (kcal/mol)
    S° = standard entropy (cal/mol*K)
    t = temperature (K) / 1000.

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Temperature (K) 298. to 600.600. to 6000.
A 2.10941014.18440
B 29.96300-0.553818
C -30.949810.212839
D 12.02940-0.013355
E 0.062082-0.828763
F -45.00280-50.09931
G 52.7983071.28511
H -43.50000-43.50000
ReferenceChase, 1998Chase, 1998
Comment Data last reviewed in June, 1970 Data last reviewed in June, 1970

Reaction thermochemistry data

Go To: Top, Gas phase thermochemistry data, 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 by: John E. Bartmess

Note: Please consider using the reaction search for this species. This page allows searching of all reactions involving this species. A general reaction search form is also available. Future versions of this site may rely on reaction search pages in place of the enumerated reaction displays seen below.

Individual Reactions

(CF3- • 4294967295Methylene, difluoro-) + Methylene, difluoro- = CF3-

By formula: (CF3- • 4294967295CF2) + CF2 = CF3-

Quantity Value Units Method Reference Comment
Δr49.8 ± 2.4kcal/molN/ADeyerl, Alconcel, et al., 2001gas phase; Adiabatic EA, from vibrational structure of spectrum
Δr50.9 ± 2.9kcal/molN/ABartmess, 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
Δr55.9 ± 2.7kcal/molCIDTPaulino and Squires, 1991gas phase; Neutral heat is based on a fluoroform acidity that may be too weak by up to 5 kcal/mol

(CAS Reg. No. 53959-80-1 • 4294967295Methylene, difluoro-) + Methylene, difluoro- = CAS Reg. No. 53959-80-1

By formula: (CAS Reg. No. 53959-80-1 • 4294967295CF2) + CF2 = CAS Reg. No. 53959-80-1

Quantity Value Units Method Reference Comment
Δr<8.00kcal/molCIDTPaulino and Squires, 1991, 2gas phase; Probably CF2..Cl-, non-covalent.

Vibrational and/or electronic energy levels

Go To: Top, Gas phase thermochemistry data, Reaction thermochemistry 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:   B ?


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

To = 72740 T gas B-X 131 138 Mathews, 1967

State:   A


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

To = 37216 gas A-X 220 380 Venkateswarlu, 1950
Laird, Andrews, et al., 1950
Mann and Thrush, 1960
Thrush and Zwolenik, 1963
Mathews, 1967
King, Schenck, et al., 1979
Cameron, Kable, et al., 1995
Wang, Chen, et al., 1998
To = 37219 ± 2 Ne Bondybey, 1976
To = 36878 ± 2 Ar A-X 210 346 Bass and Mann, 1962
Milligan, Mann, et al., 1964
Smith, Jacox, et al., 1976
Bondybey, 1976
To = 37054 ± 2 N2 Bondybey, 1976


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

a1 1 Sym. stretch 1012.1 ± 0.5 gas LF Cameron, Kable, et al., 1995
Wang, Chen, et al., 1998
2 Bend 496.7 ± 0.5 gas UV LF Venkateswarlu, 1950
Laird, Andrews, et al., 1950
Mann and Thrush, 1960
Thrush and Zwolenik, 1963
Mathews, 1967
Wang, Chen, et al., 1998
2 Bend 496 ± 2 Ne LF Bondybey, 1976
2 Bend 496 ± 2 Ar AB Bass and Mann, 1962
Milligan, Mann, et al., 1964
Smith, Jacox, et al., 1976
2 Bend 496 ± 2 Ar LF Bondybey, 1976
2 Bend 496 ± 2 N2 LF Bondybey, 1976
b2 3 Asym. stretch 1180.2 ± 0.5 gas LF Cameron, Kable, et al., 1995
Wang, Chen, et al., 1998

State:   a


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

To = 19828 gas a-X 430 800 Koda, 1978
Koda, 1979
Toby and Toby, 1980
Koda, 1982
Zhou, Zhan, et al., 1985
Murray, Leopold, et al., 1988
Schwartz, Davico, et al., 1999


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

a1 1 Sym. stretch 1020 ± 30 gas PE Schwartz, Davico, et al., 1999
2 Bend 517 gas CL Koda, 1978
Toby and Toby, 1980
Koda, 1982
Zhou, Zhan, et al., 1985
Schwartz, Davico, et al., 1999

State:   B


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

2 Bend 625 gas AB Mathews, 1967

State:   X


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

a1 1 Sym. stretch 1225.08 gas DL IR Davies, Lewis-Bevan, et al., 1981
Orlando, Reid, et al., 1987
Burkholder, Howard, et al., 1988
Wormhoudt, McCurdy, et al., 1989
1 Sym. stretch 1225.08 gas PE Murray, Leopold, et al., 1988
1 Sym. stretch 1221.9 Ne IR LF Snelson, 1970
Bondybey, 1976
Forney, Jacox, et al., 1994
1 Sym. stretch 1222 vs Ar IR LF Milligan, Mann, et al., 1964
Milligan and Jacox, 1968
Bondybey, 1976
2 Bend 666.25 gas UV DL Venkateswarlu, 1950
Mathews, 1967
Murray, Leopold, et al., 1988
Qian and Davies, 1995
2 Bend 668 w Ar IR LF Milligan, Mann, et al., 1964
Milligan and Jacox, 1968
Bondybey, 1976
b2 3 Asym.stretch 1114.44 gas IR DL Herr and Pimentel, 1965
Lefohn and Pimentel, 1971
Davies, Hamilton, et al., 1983
Burkholder, Howard, et al., 1988
Suto and Steinfeld, 1990
3 Asym.stretch 1105.8 Ne IR Snelson, 1970
Forney, Jacox, et al., 1994
3 Asym. stretch 1102 vs Ar IR Milligan, Mann, et al., 1964
Milligan and Jacox, 1968

Additional references: Jacox, 1994, page 97; Jacox, 1998, page 196; Jacox, 2003, page 137; Powell and Lide, 1966; Mathews, 1966; Basco and Hathorn, 1971; Kirchhoff, Lide, et al., 1973; Akins, King, et al., 1979; Duignan, Hudgens, et al., 1982; Charo and De Lucia, 1982; Hack and Langel, 1983; Hack and Wilms, 1986; Booth and Hancock, 1988; Ibuki, Hiraya, et al., 1989; Hermann, 1990; Creasey, Lambert, et al., 1990; Cameron and Kable, 1998; Hansen, Mader, et al., 2000

Notes

wWeak
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 thermochemistry data, Reaction thermochemistry 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.

Chase, 1998
Chase, M.W., Jr., NIST-JANAF Themochemical Tables, Fourth Edition, J. Phys. Chem. Ref. Data, Monograph 9, 1998, 1-1951. [all data]

Ehlert, 1969
Ehlert, T.C., Bonding in C1 and C2 fluroides, J. Phys. Chem., 1969, 73, 949-953. [all data]

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]

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]

Paulino and Squires, 1991, 2
Paulino, J.A.; Squires, R.R., Carbene Anion Complexes - Unusual Structural and Thermochemical Features of alpha-Halocarbanions in the Gas Phase, J. Am. Chem. Soc., 1991, 113, 5, 1845, https://doi.org/10.1021/ja00005a067 . [all data]

Mathews, 1967
Mathews, C.W., THE ABSORPTION SPECTRUM OF CF, Can. J. Phys., 1967, 45, 7, 2355, https://doi.org/10.1139/p67-188 . [all data]

Venkateswarlu, 1950
Venkateswarlu, P., On the Emission Bands of CF2, Phys. Rev., 1950, 77, 5, 676, https://doi.org/10.1103/PhysRev.77.676 . [all data]

Laird, Andrews, et al., 1950
Laird, R.K.; Andrews, E.B.; Barrow, R.F., The absorption spectrum of CF2, Trans. Faraday Soc., 1950, 46, 803, https://doi.org/10.1039/tf9504600803 . [all data]

Mann and Thrush, 1960
Mann, D.E.; Thrush, B.A., On the Absorption Spectrum of CF2 and Its Vibrational Analysis, J. Chem. Phys., 1960, 33, 6, 1732, https://doi.org/10.1063/1.1731493 . [all data]

Thrush and Zwolenik, 1963
Thrush, B.A.; Zwolenik, J.J., Predissociation in the absorption spectra of CF and CF2, Trans. Faraday Soc., 1963, 59, 582, https://doi.org/10.1039/tf9635900582 . [all data]

King, Schenck, et al., 1979
King, D.S.; Schenck, P.K.; Stephenson, J.C., Spectroscopy and photophysics of the CF2 system, J. Mol. Spectrosc., 1979, 78, 1, 1, https://doi.org/10.1016/0022-2852(79)90031-6 . [all data]

Cameron, Kable, et al., 1995
Cameron, M.R.; Kable, S.H.; Bacskay, G.B., The electronic spectroscopy of jet-cooled difluorocarbene (CF2): The missing A-state stretching frequencies, J. Chem. Phys., 1995, 103, 11, 4476, https://doi.org/10.1063/1.470728 . [all data]

Wang, Chen, et al., 1998
Wang, C.; Chen, C.; Dai, J.; Ma, X., Laser-induced fluorescence studies of jet-cooled CF2: determination of Ã-state stretching frequencies, Chem. Phys. Lett., 1998, 288, 2-4, 473, https://doi.org/10.1016/S0009-2614(98)00275-9 . [all data]

Bondybey, 1976
Bondybey, V.E., Vibrationally unrelaxed fluorescence in matrix isolated CF2, J. Mol. Spectrosc., 1976, 63, 2, 164, https://doi.org/10.1016/0022-2852(76)90002-3 . [all data]

Bass and Mann, 1962
Bass, A.M.; Mann, D.E., Absorption Spectrum of CF2 Trapped in an Argon Matrix, J. Chem. Phys., 1962, 36, 12, 3501, https://doi.org/10.1063/1.1732492 . [all data]

Milligan, Mann, et al., 1964
Milligan, D.E.; Mann, D.E.; Jacox, M.E.; Mitsch, R.A., Infrared Spectrum of CF2, J. Chem. Phys., 1964, 41, 5, 1199, https://doi.org/10.1063/1.1726051 . [all data]

Smith, Jacox, et al., 1976
Smith, C.E.; Jacox, M.E.; Milligan, D.E., The absorption and fluorescence spectra of matrix-isolated CF2, J. Mol. Spectrosc., 1976, 60, 1-3, 381, https://doi.org/10.1016/0022-2852(76)90141-7 . [all data]

Koda, 1978
Koda, S., Emission and energy transfer of triplet difluoromethylene produced in the reaction of oxygen atoms with tetrafluoroethylene, Chem. Phys. Lett., 1978, 55, 2, 353, https://doi.org/10.1016/0009-2614(78)87037-7 . [all data]

Koda, 1979
Koda, S., Mechanism of oxygen (3P) atom reaction with tetrafluoroethylene and quenching processes of the emission of difluoromethylene (3B1), J. Phys. Chem., 1979, 83, 16, 2065, https://doi.org/10.1021/j100479a004 . [all data]

Toby and Toby, 1980
Toby, S.; Toby, F.S., Singlet and triplet emission from difluoromethylene in the reaction of ozone with tetrafluorethene, J. Phys. Chem., 1980, 84, 2, 206, https://doi.org/10.1021/j100439a016 . [all data]

Koda, 1982
Koda, S., Initial vibrational distribution and relaxation of 3CF2 produced in the reaction of oxygen atoms with tetrafluoroethylene, Chem. Phys., 1982, 66, 3, 383, https://doi.org/10.1016/0301-0104(82)88038-5 . [all data]

Zhou, Zhan, et al., 1985
Zhou, S.; Zhan, M.; Qiu, Y.; Liu, S.; Shi, J.; Li, F.; Yao, J., Chemiluminescence of CF2(3B1) produced by the reaction O(3P) + C2F4, Chem. Phys. Lett., 1985, 121, 4-5, 395, https://doi.org/10.1016/0009-2614(85)87201-8 . [all data]

Murray, Leopold, et al., 1988
Murray, K.K.; Leopold, D.G.; Miller, T.M.; Lineberger, W.C., Photoelectron Spectroscopy of the Halocarbene Anions HCF-, HCCl-, HCBr-, HCI-, CF2-, and CCl2-, J. Chem. Phys., 1988, 89, 9, 5442, https://doi.org/10.1063/1.455596 . [all data]

Schwartz, Davico, et al., 1999
Schwartz, R.L.; Davico, G.E.; Ramond, T.M.; Lineberger, W.C., Singlet-Triplet Splittings in CX, J. Phys. Chem. A, 1999, 103, 41, 8213, https://doi.org/10.1021/jp992214c . [all data]

Davies, Lewis-Bevan, et al., 1981
Davies, P.B.; Lewis-Bevan, W.; Russell, D.K., Infrared diode laser spectrum of the ν1 band of CF2 (X 1A1), J. Chem. Phys., 1981, 75, 12, 5602, https://doi.org/10.1063/1.441998 . [all data]

Orlando, Reid, et al., 1987
Orlando, J.J.; Reid, J.; Smith, D.R., Time-resolved tunable diode laser detection of products of CF2HCl IRMPD: A linestrength measurement for CF2, Chem. Phys. Lett., 1987, 141, 5, 423, https://doi.org/10.1016/0009-2614(87)85053-4 . [all data]

Burkholder, Howard, et al., 1988
Burkholder, J.B.; Howard, C.J.; Hamilton, P.A., Fourier transform spectroscopy of the ν1 and ν3 fundamental bands of CF2, J. Mol. Spectrosc., 1988, 127, 2, 362, https://doi.org/10.1016/0022-2852(88)90126-9 . [all data]

Wormhoudt, McCurdy, et al., 1989
Wormhoudt, J.; McCurdy, K.E.; Burkholder, J.B., Measurements of the strengths of infrared bands of CF2, Chem. Phys. Lett., 1989, 158, 6, 480, https://doi.org/10.1016/0009-2614(89)87374-9 . [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 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]

Qian and Davies, 1995
Qian, H.-B.; Davies, P.B., Infrared Laser Spectroscopy of the ν2 Band of Difluorocarbene (CF2), J. Mol. Spectrosc., 1995, 169, 1, 201, https://doi.org/10.1006/jmsp.1995.1016 . [all data]

Herr and Pimentel, 1965
Herr, K.C.; Pimentel, G.C., A Rapid-Scan Infrared Spectrometer; Flash Photolytic Detection of Chloroformic Acid and of CF_2, Appl. Opt., 1965, 4, 1, 25, https://doi.org/10.1364/AO.4.000025 . [all data]

Lefohn and Pimentel, 1971
Lefohn, A.S.; Pimentel, G.C., Infrared Spectrum of Gaseous CF2 by Rapid Scan Spectroscopy, J. Chem. Phys., 1971, 55, 3, 1213, https://doi.org/10.1063/1.1676207 . [all data]

Davies, Hamilton, et al., 1983
Davies, P.B.; Hamilton, P.A.; Elliott, J.M.; Rice, M.J., Infrared diode laser spectroscopy of the ν3 band of CF2, J. Mol. Spectrosc., 1983, 102, 1, 193, https://doi.org/10.1016/0022-2852(83)90237-0 . [all data]

Suto and Steinfeld, 1990
Suto, O.; Steinfeld, J., Time-resolved diode laser absorption spectroscopy of CF2 produced in UV photodissociation of C2F4 and measurement of ν3 absorption band strength, Chem. Phys. Lett., 1990, 168, 2, 181, https://doi.org/10.1016/0009-2614(90)85126-W . [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]

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]

Powell and Lide, 1966
Powell, F.X.; Lide, D.R., Jr., Microwave Spectrum of CF2, J. Chem. Phys., 1966, 45, 3, 1067, https://doi.org/10.1063/1.1727662 . [all data]

Mathews, 1966
Mathews, C.W., 2500-… Absorption Spectrum of CF2, J. Chem. Phys., 1966, 45, 3, 1068, https://doi.org/10.1063/1.1727663 . [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]

Kirchhoff, Lide, et al., 1973
Kirchhoff, W.H.; Lide, D.R., Jr.; Powell, F.X., The microwave spectrum, force field and dipole moment of CF2, J. Mol. Spectrosc., 1973, 47, 3, 491, https://doi.org/10.1016/0022-2852(73)90096-9 . [all data]

Akins, King, et al., 1979
Akins, D.L.; King, D.S.; Stephenson, J.C., Vibrational relaxation of CF2(ν2 = 1--6 in non-reactive collisions, Chem. Phys. Lett., 1979, 65, 2, 257, https://doi.org/10.1016/0009-2614(79)87060-8 . [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]

Charo and De Lucia, 1982
Charo, A.; De Lucia, F.C., The millimeter and submillimeter spectrum of CF2 and its production in a dc glow discharge, J. Mol. Spectrosc., 1982, 94, 2, 363, https://doi.org/10.1016/0022-2852(82)90012-1 . [all data]

Hack and Langel, 1983
Hack, H.; Langel, W., Photophysics of difluoromethylene (~A 1B1 (0,6,0)) excited by a krypton fluoride laser at 248 nm. 3. Direct measurements of 1B1 collisional removal rates, J. Phys. Chem., 1983, 87, 18, 3462, https://doi.org/10.1021/j100241a022 . [all data]

Hack and Wilms, 1986
Hack, W.; Wilms, A., Photophysics of difluoromethylene (A1B1(0,2,0)). 4. Deactivation processes for single rotational states, J. Phys. Chem., 1986, 90, 17, 4007, https://doi.org/10.1021/j100408a036 . [all data]

Booth and Hancock, 1988
Booth, J.P.; Hancock, G., The radiative lifetime of CF(A 2Σ+), Chem. Phys. Lett., 1988, 150, 5, 457, https://doi.org/10.1016/0009-2614(88)87229-4 . [all data]

Ibuki, Hiraya, et al., 1989
Ibuki, T.; Hiraya, A.; Shobatake, K., Photochemistry of CCl3F and CCl2F2 in the 106--200 nm region, J. Chem. Phys., 1989, 90, 11, 6290, https://doi.org/10.1063/1.456345 . [all data]

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

Cameron and Kable, 1998
Cameron, M.R.; Kable, S.H., Rotational State Dependent Fluorescence Lifetimes in CF2, J. Mol. Spectrosc., 1998, 192, 2, 449, https://doi.org/10.1006/jmsp.1998.7698 . [all data]

Hansen, Mader, et al., 2000
Hansen, N.; Mader, H.; Temps, F., Nuclear spin--rotation interaction in CF2 () observed by Fourier transform microwave spectroscopy, Chem. Phys. Lett., 2000, 327, 1-2, 97, https://doi.org/10.1016/S0009-2614(00)00840-X . [all data]


Notes

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