Phosphinidene


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: John E. Bartmess

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Individual Reactions

(CAS Reg. No. 13937-34-3 • 4294967295Phosphinidene) + Phosphinidene = CAS Reg. No. 13937-34-3

By formula: (CAS Reg. No. 13937-34-3 • 4294967295HP) + HP = CAS Reg. No. 13937-34-3

Quantity Value Units Method Reference Comment
Δr91.7 ± 8.1kcal/molN/AErvin and Lineberger, 2005gas phase; High level calcns( Curtiss, Raghavachari, et al., 1991, Ricca and Bauschlicher, 1998) give DH ca. 84
Δr84.7 ± 2.9kcal/molTherBartmess, Scott, et al., 1979gas phase; The D-EA cycle does not close by 7 kcal/mol. The reason for this discrepancy is not known; value altered from reference due to change in acidity scale

P- + Hydrogen cation = Phosphinidene

By formula: P- + H+ = HP

Quantity Value Units Method Reference Comment
Δr367.7 ± 8.0kcal/molD-EAAndersson, Lindahl, et al., 2007gas phase
Quantity Value Units Method Reference Comment
Δr362.0 ± 8.1kcal/molH-TSAndersson, Lindahl, et al., 2007gas phase

Constants of diatomic molecules

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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: Klaus P. Huber and Gerhard H. Herzberg

Data collected through July, 1977

Symbols used in the table of constants
SymbolMeaning
State electronic state and / or symmetry symbol
Te minimum electronic energy (cm-1)
ωe vibrational constant – first term (cm-1)
ωexe vibrational constant – second term (cm-1)
ωeye vibrational constant – third term (cm-1)
Be rotational constant in equilibrium position (cm-1)
αe rotational constant – first term (cm-1)
γe rotation-vibration interaction constant (cm-1)
De centrifugal distortion constant (cm-1)
βe rotational constant – first term, centrifugal force (cm-1)
re internuclear distance (Å)
Trans. observed transition(s) corresponding to electronic state
ν00 position of 0-0 band (units noted in table)
Diatomic constants for 31PH
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
d 1Π     [8.478] 1   [4.17E-4]  [1.4273] d ← a 62725.28 Z
missing citation
B 3Π0     [7.3]     [1.54] B ← X R 69587.8 Z
Balfour and Douglas, 1968
c 1Φ     [8.602] 0.21  [5.44E-4]  [1.4170] c ← a 2 61548.68 Z
missing citation
A 3Πi,0+ 29498 3 [1833.78] Z (98.5) 4  [8.0222] 5 6  [5.683E-4] 7  [1.46728] A ↔ X 8 R 29434.61 9
missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
A 3Πi,0- 29498 3 [1833.39] Z (98.5) 4  [8.0222] 5 6  [5.683E-4] 7  [1.46728] A ↔ X 8 R 29434.28 9
missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
A 3Πi,1 29498 3 [1833.74] Z (98.5) 4  [8.0222] 5 6  [5.683E-4] 7  [1.46728] A ↔ X 8 R 29316.81 9
missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
A 3Πi,2 29498 3 [1834.38] Z (98.5) 4  [8.0222] 5 6  [5.683E-4] 7  [1.46728] A ↔ X 8 R 29203.21 9
missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
b 1Σ+ (15160) 10           
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
a 1Δ (7660) 10    [8.443] 0.12  [4.18E-4]  [1.4302] 11  
Davies, Russell, et al., 1975
X 3Σ- 0 2365.2 12 44.5 12  8.5371 13 0.2514  4.36E-4  1.42234 11  
Davies, Russell, et al., 1975

Notes

1Λ-type doubling |Δv| = 0.1275J(J+l) - 0.54E-4J2(J+1)2.
2Sequence of nearly undegraded bands; the origins of the 1-1 and 2-2 bands are at 61554.5 and 61560.7 cm-1, respectively.
3A0 = -115.71, A1 = -115.20; see Rostas, Cossart, et al., 1974 who give also centrifugal distortion corrections AD as well as estimated spin-spin and second-order spin-orbit parameters.
4Estimated using isotope relations.
5For Λ-doubling constants see Rostas, Cossart, et al., 1974.
6B1 = 7.5492. No emission has been observed from v=1 of PH, probably owing to weak predissociation by the repulsive 5Σ- state arising from ground state atoms Rostas, Cossart, et al., 1974.
7D1 = 6.54E-4, H0 = -1.6E-8.
8Lifetime τ= 0.45 μs, corresponding to an absorption oscillator strength of 0.0078 Fink and Welge, 1964.
9Subband origins as defined by Rostas, Cossart, et al., 1974.
10Theoretical predictions Jordan, 1964, Cade, 1968, Liu, Legentil, et al., 1972, for a 1Δ confirmed by laser photoelectron spectrometry of PH-[see ref. Ishaque and Pearse, 1939 of PH-).
11Rotation sp. 15
12Constants deduced from isotope relations Rostas, Cossart, et al., 1974.
13Spin splitting constants λ0 = +2.212, γ0 = -0.0738; λ1 = +2.207, γ1 = -0.0726 Rostas, Cossart, et al., 1974.
14Adjusted theoretical value recommended by Meyer and Rosmus, 1975; see also Jordan, 1964, Cade and Huo, 1967, Liu, Legentil, et al., 1972.
15N=4→5 rotational transitions observed by the laser magnetic resonance method.
16From the value for PH.
17A0= -115.74, A1= -115.55; see also 3.
18B1= 4.0047.
19D1= 1.640E-4.
20Spin splitting constants λ0= +2.211, γ0= -0.0385; λ1= +2.202, γ1= 0.0381 Rostas, Cossart, et al., 1974.

References

Go To: Top, Reaction thermochemistry data, Constants of diatomic molecules, Notes

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

Ervin and Lineberger, 2005
Ervin, K.M.; Lineberger, W.C., Photoelectron spectroscopy of phosphorus hydride anions, J. Chem. Phys., 2005, 122, 19, 194303, https://doi.org/10.1063/1.1881153 . [all data]

Curtiss, Raghavachari, et al., 1991
Curtiss, L.A.; Raghavachari, K.; Trucks, G.W.; Pople, J.A., Gaussian-2 Theory for Molecular Energies of First- and Second-row Compounds, J. Chem. Phys., 1991, 94, 11, 7221, https://doi.org/10.1063/1.460205 . [all data]

Ricca and Bauschlicher, 1998
Ricca, A.; Bauschlicher, C.W., Jr., Accurate Heats of Formation for PHn, PHn+, and PHn-, Chem. Phys. Lett., 1998, 285, 5-6, 455, https://doi.org/10.1016/S0009-2614(97)01468-1 . [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]

Andersson, Lindahl, et al., 2007
Andersson, P.; Lindahl, A.O.; Alfredsson, C.; Rogstrom, L.; Diehl, C.; Pegg, D.J.; Hanstorp, D., The electron affinity of phosphorus, J. Phys. B - Atom. Mol. Opt. Phys., 2007, 40, 20, 4097-4107, https://doi.org/10.1088/0953-4075/40/20/010 . [all data]

Balfour and Douglas, 1968
Balfour, W.J.; Douglas, A.E., The absorption spectrum of PH in the vacuum ultraviolet, Can. J. Phys., 1968, 46, 2277. [all data]

Horani, Rostas, et al., 1967
Horani, M.; Rostas, J.; Lefebvre-Brion, H., Find structure of 3Σ- and 3Π states of NH, OH+, PH, and SH+, Can. J. Phys., 1967, 45, 3319. [all data]

Rostas, Cossart, et al., 1974
Rostas, J.; Cossart, D.; Bastien, J.R., Rotational analysis of the PH and PD A3Πi-X3Σ- band systems, Can. J. Phys., 1974, 52, 1274. [all data]

Davies, Russell, et al., 1975
Davies, P.B.; Russell, D.K.; Thrush, B.A., Laser magnetic resonance spectra of the PH radical, Chem. Phys. Lett., 1975, 36, 280. [all data]

Fink and Welge, 1964
Fink, E.; Welge, K.H., Lebensdauer der Elektronenzustande N2(C3Πu), N2+(B2Σu+), NH(A3Π), NH(c1Π), PH(3Π), Z. Naturforsch. A, 1964, 19, 1193. [all data]

Jordan, 1964
Jordan, P.C., Lower electronic levels of the radicals PH and PH2, J. Chem. Phys., 1964, 41, 1442. [all data]

Cade, 1968
Cade, P.E., Theoretical prediction of the singlet-triplet intercombination separations for NH, OH+, PH, and SH+, Can. J. Phys., 1968, 46, 1989. [all data]

Liu, Legentil, et al., 1972
Liu, H.P.D.; Legentil, J.; Verhaegen, G., Calculated energy levels of some diatomic hydrides in Selected Topics in Molecular Physics [Proceedings of the national symposium at Ludwigsburg (Germany)], Clementi; Chemie GmbH, ed(s)., Weinheim, Bergstr., 1972, 19-33. [all data]

Ishaque and Pearse, 1939
Ishaque, M.; Pearse, R.W.B., The λ3400 bands of PH and PD, Proc. R. Soc. London A, 1939, 173, 265. [all data]

Meyer and Rosmus, 1975
Meyer, W.; Rosmus, P., PNO-Cl and CEPA studies of electron correlation effects. III. Spectroscopic constants and dipole moment functions for the ground states of the first-row and second-row diatomic hydrides, J. Chem. Phys., 1975, 63, 2356. [all data]

Cade and Huo, 1967
Cade, P.E.; Huo, W.M., Electronic structure of diatomic molecules. VII.A. Hartree-Fock wavefunctions and energy quantities for the ground states of the second-row hydrides, AH, J. Chem. Phys., 1967, 47, 649. [all data]


Notes

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