Phosphorus monoxide

Gas phase 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.

Quantity Value Units Method Reference Comment
ΔfH°gas-23.55kJ/molReviewChase, 1998Data last reviewed in June, 1971
Quantity Value Units Method Reference Comment
S°gas,1 bar222.78J/mol*KReviewChase, 1998Data last reviewed in June, 1971

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 (J/mol*K)
    H° = standard enthalpy (kJ/mol)
    S° = standard entropy (J/mol*K)
    t = temperature (K) / 1000.

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Temperature (K) 298. to 600.600. to 6000.
A 24.2856135.82830
B 18.864651.413825
C -1.520015-0.322620
D -7.3659320.030065
E 0.194004-0.951312
F -30.94863-36.97384
G 247.7652261.7816
H -23.54801-23.54801
ReferenceChase, 1998Chase, 1998
Comment Data last reviewed in June, 1971 Data last reviewed in June, 1971

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 September, 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 31P16O
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
Theoretical calculations of the ground state Boyd and Lipscomb, 1967 Mulliken and Liu, 1971, of low-lying valence states Roche and Lefebvre-Brion, 1973 Tseng and Grein, 1973, and of Rydberg states Ackermann, Lefebvre-Brion, et al., 1972.
H 2Σ+ (56017) 1 (1391) (7)  (0.780) (0.0054)    (1.431) H → B RV (25401) 2
↳missing citation; Ngo, da Paz, et al., 1974
I 2Σ+ 55458.1 1390.2 Z 6.0  0.7798 3 0.0048  0.8E-6  1.4316 I → A 15051.1 Z
↳missing citation
           I → B V 24842.0
↳missing citation; missing citation
           I → X V 55536.7
↳missing citation
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
E 2Δ 53091 [1456.28] Z (15.8)  0.7583 4 0.0074  0.8E-6  1.4518 E → X V 53215.6 Z
↳missing citation; missing citation; missing citation
G 2Σ+ (52412) 1 (1382) (13)  (0.780) (0.0054)    (1.431) G → A (11999) 2
↳missing citation
           G → B RV (21790) 2
↳missing citation; missing citation
           G → X V (52484) 2
↳missing citation
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
F 2Σ+ (49880) 1 (850) (7.5)  (0.6082) (0.0045)    (1.621) F → A R (9202) 2
↳missing citation
           F → B R (18993) 2
↳missing citation; Guha, Jois, et al., 1972; missing citation
           F → X R (49688) 2
↳missing citation
D 2Πr 48520 5 [1358.1] (7)  0.755 6 0.007    1.455 D → B R 17894.6 2
↳Couet, Coquart, et al., 1968; missing citation; missing citation
           D ↔ X R 48589.3 2
↳Dressler, 1955; Couet, Coquart, et al., 1968; missing citation; missing citation
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
C 2Σ- 44831.75 779.22 7 Z 5.14  0.5903 7 0.0056  (1.4E-6)  1.645 C → X R 44605.05 Z
↳Dressler, 1955; Verma and Broida, 1970; missing citation; missing citation
C' 2Δ 43742.74 825.74 Z 6.93 8  0.6405 9 0.0052  (1.5E-6)  1.580 C' → X R 43538.85 Z
↳Santaram and Rao, 1962; Narasimham, Dixit, et al., 1966; missing citation; Dixit and Narasimham, 1969; Verma and Broida, 1970; missing citation; missing citation
A 2Σ+ 40406.89 1390.94 10 Z 6.91 10  0.7801 10 11 12 0.00542 10  1.0E-6  1.4313 A → B VR 9790.86 Z
↳missing citation; missing citation; missing citation
           A ↔ X 13 V 40485.60 Z
↳missing citation; Norrish and Oldershaw, 1961; Coquart, Couet, et al., 1967; missing citation; missing citation
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
B' 2Π 33120.7 14 759.2 15 3.85 15  0.5420 15 0.0049 15  [1.0E-6]  1.7172 B' → B 16 R 
↳missing citation
           B' ↔ X R 32884.3 15
↳Verma, 1970; Verma and Broida, 1970; Verma and Singhal, 1975; missing citation
b 4Σ- (34837) 17 (889.0) 17 (6.62) 17  (0.644) 17 (0.006) 17    (1.575)  
B 2Σ+ 30730.88 1164.51 Z 13.46 -0.05 0.7463 18 12 0.0088 -0.00006 1.25E-6  1.4634 B ↔ X VR 30694.74 Z
↳missing citation; Norrish and Oldershaw, 1961; missing citation; Couet, Tuan Anh, et al., 1968; missing citation; Rai, Rai, et al., 1972; missing citation; missing citation
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
X 2Πr 0 19 1233.34 Z 6.56  0.7337 20 12 0.0055  1.3E-6  1.4759  

Notes

1The G, H, I 2Σ+ Rydberg states (as well as higher levels of A 2Σ+) interact with the F 2Σ+ non-Rydberg state. Most of the observed bands are strongly perturbed. The constants in the Table are deperturbed values taken from Ngo, da Paz, et al., 1974 who give results for P16O and P18O; similar constants have earlier been reported by Verma, Dixit, et al., 1971. In addition to the strong homogeneous interactions a large number of local perturbations have been described for both isotopes Verma, Dixit, et al., 1971, Guha, Jois, et al., 1972, Ngo, da Paz, et al., 1974.
2The v00 values have been calculated from deperturbed constants and should not be expected to coincide precisely with observed transitions.
3Rotational perturbations in v=0,1,2 Guha, Jois, et al., 1972.
4Perturbations by C' 2Δ.
5A0 = +26.2, A1 = +22.8. All constants given for D 2Π (v=0,1) are deperturbed values from Ghosh, Nagaraj, et al., 1976; see also Coquart, da Paz, et al., 1974. This state interacts strongly with high vibrational levels of B' 2Π. For v=2 and 3 only fragments have been observed in absorption Ghosh, Nagaraj, et al., 1976 making the deperturbation results for these levels even less reliable.
6The highest level observed in emission from the interacting pair D(v=0) ~ B'(v=24?) is the N=34 level [predominantly D(v=0)] lying at 49647 cm-1 above X 2Π1/2(v=0,J=1/2); see Couet, Coquart, et al., 1968. Higher levels are predissociated and give rise to diffuse lines in the absorption spectrum. A summary of predissociation phenomena observed in B' and D levels is given by Ghosh, Nagaraj, et al., 1976 who suggest that the predissociation is caused by the repulsive part of the 4Π state arising from 4S + 3P.
7missing note
8 Prudhomme and Coquart, 1974 suggest that an additional term, weye ~ 0.040, is needed in order to account for higher vibrational levels (v=l4...18) found in perturbations of E 2Δ(v=0,1,2).
9Small spin doubling, γ ~ 0.0085 Prudhomme, Larzilliere, et al., 1973; local perturbations.
10Average of values obtained by Rao, 1958, Verma and Jois, 1973, Coquart, da Paz, et al., 1975. Above v=3 the influence of the F 2Σ+ state becomes noticeable.
11Spin splitting constant γ ~ +0.0013 Verma and Jois, 1973. Many rotational perturbations Coquart and Prudhomme, 1972, Verma and Jois, 1973, Coquart, da Paz, et al., 1975.
12Potentia1 curves Singh and Rai, 1965.
13Franck-Condon factors Sankaranarayanan, 1966.
14Av increases from -13.3 for v=0 to about +30 for v=23...26 Verma, 1970, Coquart, da Paz, et al., 1974, Ghosh, Nagaraj, et al., 1976; theoretical explanation Roche and Lefebvre-Brion, 1973.
15These are the constants of Verma and Jois, 1973 based on the rotational analysis of v=0 and 1 Verma, 1970 and on the identification of several intermediate levels (v=6 and 12...22) in perturbations with B 2Σ+ Verma and Singhal, 1975 and A 2Σ+ Verma and Jois, 1973. Higher vibrational levels (v=23...26, formerly D' 2Π) are observed in the region of strong interaction with the Rydberg D 2Π state Coquart, da Paz, et al., 1974, Ghosh, Nagaraj, et al., 1976. The vibrational numbering chosen by Verma, 1970 and used in this Table is arbitrary and may have to be increased by 2 as suggested by Cornet, Dubois, et al., 1977 whose re-analysis of the B'-X system includes a large number of absorption bands previously attributed to OPCl Verma and Nagaraj, 1975 as well as a number of emission bands left unassigned by Verma and Broida, 1970 and Verma and Singhal, 1975.
16The B'→B bands originate from highly excited levels with v' ~ 24 which are strongly mixed with low vibrational levels of D 2Π.
17Constants derived from perturbations in B 2Σ+ and A 2Σ+ Verma and Singhal, 1975, corrected for the new vibrational numbering of Coquart, da Paz, et al., 1975.
18Spin splitting constant γ = -0.0068. Extensive rotational perturbations in v=6,7 by levels of B' 2Π and b 4Σ-; see Verma and Singhal, 1975. The v=7 level appears to be preferentially populated in the P4 + O glow Verma and Broida, 1970.
19Av = 224.03 + 0.18v - 0.013v2 (v≤11) Verma and Singhal, 1975; see also Zaidi and Verma, 1975. Similar results in Prudhomme, Larzilliere, et al., 1973.
20Λ-type doubling Δvef(2Π1/2) = -0.0070(J+1/2).
21Thermochemical value (mass-spectrometry) Drowart, Myers, et al., 1972. The predissociation in the perturbed D(v=0) level (see 6) gives the upper limit D00 ≤ 6.161 eV.
22Theoretical value Ackermann, Lefebvre-Brion, et al., 1972. Drowart, Myers, et al., 1972 report an electron impact appearance potential of 8.5 eV.
23Vibrational numbering confirmed by P16O - P18O isotope shifts Prudhomme, Larzilliere, et al., 1973.
24Papers by Singh, 1959, Mohanty, Upadhya, et al., 1967, Mohanty, Rai, et al., 1969 contain erroneous branch identifications; see Verma and Dixit, 1968, Rai, Rai, et al., 1972.

References

Go To: Top, Gas phase 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.

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

Boyd and Lipscomb, 1967
Boyd, D.B.; Lipscomb, W.N., Molecular SCF calculations on PH3, PO, PO-, and P2, J. Chem. Phys., 1967, 46, 910. [all data]

Mulliken and Liu, 1971
Mulliken, R.S.; Liu, B., Self-consistent-field wave functions of P2 and PO, and the role of d functions in chemical bonding and of s-p hybridization in N2 and P2, J. Am. Chem. Soc., 1971, 93, 6738. [all data]

Roche and Lefebvre-Brion, 1973
Roche, A.L.; Lefebvre-Brion, H., Valence-shell states of PO: an example of the variation of the spin-orbit coupling constants with internuclear distance, J. Chem. Phys., 1973, 59, 1914. [all data]

Tseng and Grein, 1973
Tseng, T.J.; Grein, F., Low-lying valence states of the PO molecule according to configuration-interaction calculations, J. Chem. Phys., 1973, 59, 6563. [all data]

Ackermann, Lefebvre-Brion, et al., 1972
Ackermann, F.; Lefebvre-Brion, H.; Roche, A.L., Calculated Rydberg states of the PO molecule, Can. J. Phys., 1972, 50, 692. [all data]

Ngo, da Paz, et al., 1974
Ngo, T.A.; da Paz, M.; Coquart, B.; Couet, C., Spectre d'emission de la molecule PO: etude des etats 2Σ+ situes dans le domaine energetique 50 000-58 000 cm-1 des molecules P16O et P18O, Can. J. Phys., 1974, 52, 154. [all data]

Guha, Jois, et al., 1972
Guha, S.; Jois, S.S.; Verma, R.D., Emission spectrum of the PO molecule. Part III. Spectrum in the red region, Can. J. Phys., 1972, 50, 1579. [all data]

Couet, Coquart, et al., 1968
Couet, C.; Coquart, B.; Tuan Anh, N.; Guenebaut, H., Contribution a l'etude des systemes electroniques du radical PO. IV. Etude des systemes visibles et ultraviolets mettant en jeu les etats D2Πr(a) et D'2Π(a), J. Chim. Phys. Phys.-Chim. Biol., 1968, 65, 1241. [all data]

Dressler, 1955
Dressler, K., Ultraviolett- und Schumannspektren der neutralen und ionisierten Molekule PO, PS, NS, P2, Helv. Phys. Acta, 1955, 28, 563. [all data]

Verma and Broida, 1970
Verma, R.D.; Broida, H.P., Spectral study of the phosphorus glow, Can. J. Phys., 1970, 48, 2991. [all data]

Santaram and Rao, 1962
Santaram, C.V.V.S.N.K.; Rao, P.T., The band spectrum of PO: two new doublet systems in the ultraviolet, Z. Phys., 1962, 168, 553. [all data]

Narasimham, Dixit, et al., 1966
Narasimham, N.A.; Dixit, M.N.; Sethuraman, V., 2Σ → X2Π band system in PO molecule, Proc. Indian Acad. Sci. Sect. A, 1966, 62, 314. [all data]

Dixit and Narasimham, 1969
Dixit, M.N.; Narasimham, N.A., Isotope shift studies of the ultra-violet and visible bands of P16O and P18O, Proc. Indian Acad. Sci. Sect. A, 1969, 68, 1. [all data]

Norrish and Oldershaw, 1961
Norrish, R.G.W.; Oldershaw, G.A., The oxidation of phosphine studied by flash photolysis and kinetic spectroscopy, Proc. R. Soc. London A, 1961, 262, 10. [all data]

Coquart, Couet, et al., 1967
Coquart, B.; Couet, C.; Tuan Anh, N.; Guenebaut, H., Contribution a l'etude des systemes electroniques du radical PO 2e partie: considerations nouvelles sur le systeme γ (transition A2Σ+ - X2Πa), J. Chim. Phys. Phys.-Chim. Biol., 1967, 64, 1197. [all data]

Verma, 1970
Verma, R.D., Emission spectrum of the PO molecule. I. A new B'2Πi-X2Πr transition, Can. J. Phys., 1970, 48, 2391. [all data]

Verma and Singhal, 1975
Verma, R.D.; Singhal, S.R., New results on the B2Σ+, b4Σ-, and X2Π states of PO, Can. J. Phys., 1975, 53, 411. [all data]

Couet, Tuan Anh, et al., 1968
Couet, C.; Tuan Anh, N.; Coquart, B.; Guenebaut, H., Contribution a l'etude des systemes electroniques du radical PO. 3e partie: le systeme β (transition B2Σ+ - X2Πa), J. Chim. Phys. Phys.-Chim. Biol., 1968, 65, 217. [all data]

Rai, Rai, et al., 1972
Rai, S.B.; Rai, D.K.; Upadhya, K.N., Analysis of some bands of the β system of PO, J. Phys. B:, 1972, 5, 1038. [all data]

Verma, Dixit, et al., 1971
Verma, R.D.; Dixit, M.N.; Jois, S.S.; Nagaraj, S.; Singhal, S.R., Emission spectrum of the PO molecule. Part II. 2Σ-2Σ transitions, Can. J. Phys., 1971, 49, 3180. [all data]

Ghosh, Nagaraj, et al., 1976
Ghosh, S.; Nagaraj, S.; Verma, R.D., New results on the D2Π and B'2Π states of the PO molecule, Can. J. Phys., 1976, 54, 695. [all data]

Coquart, da Paz, et al., 1974
Coquart, B.; da Paz, M.; Prudhomme, J.C., Spectre d'emission de la molecule PO: transitions D2Π-B2Σ+ et D'2Π-B2Σ+ des molecules P16O et P18O. Reconsideration de l'etat de valence D'2Π, Can. J. Phys., 1974, 52, 177. [all data]

Prudhomme and Coquart, 1974
Prudhomme, J.C.; Coquart, B., Spectre d'emission de la molecule P18O: donnees nouvelles sur l'etat E2Δ, Can. J. Phys., 1974, 52, 2150. [all data]

Prudhomme, Larzilliere, et al., 1973
Prudhomme, J.C.; Larzilliere, M.; Couet, C., Spectre d'emission de la molecule PO: transitions C'2Δ-X2Πr et C2Σ--X2Πr de P16O et P18O, Can. J. Phys., 1973, 51, 2464. [all data]

Rao, 1958
Rao, K.S., Rotational analysis of the γ system of the PO molecule, Can. J. Phys., 1958, 36, 1526. [all data]

Verma and Jois, 1973
Verma, R.D.; Jois, S.S., Emission spectrum of the PO molecule. Part IV. Spectrum in the region 7000-12 000 Å, Can. J. Phys., 1973, 51, 322. [all data]

Coquart, da Paz, et al., 1975
Coquart, B.; da Paz, M.; Prudhomme, J.C., Transition A2Σ+ - X2Π des molecules P16O et P18O. Perturbations de l'etat A2Σ+, Can. J. Phys., 1975, 53, 377. [all data]

Coquart and Prudhomme, 1972
Coquart, B.; Prudhomme, J.-C., Reconsiderations sur le systeme γ de PO; localisation de perturbations rotationnelles dans les premiers niveaux vibrationnels de l'etat A2Σ+, C.R. Acad. Sci. Paris, Ser. B, 1972, 275, 383. [all data]

Singh and Rai, 1965
Singh, R.B.; Rai, D.K., Potential curves and bond strength of PO, J. Phys. Chem., 1965, 69, 3461. [all data]

Sankaranarayanan, 1966
Sankaranarayanan, S., γ-Centroids and Franck-Condon factors for the bands of A2Σ-X2Π system of PO molecule, Indian J. Phys., 1966, 40, 678. [all data]

Cornet, Dubois, et al., 1977
Cornet, R.; Dubois, I.; Houbrechts, Y., About the absorption spectrum of OPCl, J. Phys. B:, 1977, 10, 415. [all data]

Verma and Nagaraj, 1975
Verma, R.D.; Nagaraj, S., A new absorption spectrum attributable to the OPCl radical, J. Mol. Spectrosc., 1975, 58, 301. [all data]

Zaidi and Verma, 1975
Zaidi, H.R.; Verma, R.D., Quantum number dependence of the spin-orbit coupling in the X2Π state of PO, Can. J. Phys., 1975, 53, 420. [all data]

Drowart, Myers, et al., 1972
Drowart, J.; Myers, C.E.; Szwarc, R.; Vander Auwera-Mahieu, A.; Uy, O.M., Determination by the mass spectrometric Knudsen cell method of the atomization energies of the molecules PO and PO2, J. Chem. Soc. Faraday Trans. 2, 1972, 68, 1749. [all data]

Singh, 1959
Singh, N.L., Rotational analysis of the β bands of phosphorus monoxide, Can. J. Phys., 1959, 37, 136. [all data]

Mohanty, Upadhya, et al., 1967
Mohanty, B.S.; Upadhya, K.N.; Singh, R.B.; Singh, N.L., On the β-band system of the PO molecule, J. Mol. Spectrosc., 1967, 24, 19. [all data]

Mohanty, Rai, et al., 1969
Mohanty, B.S.; Rai, D.K.; Upadhya, K.N., Structure and analysis of some bands of the β-system of PO molecule, Proc. Indian Acad. Sci. Sect. A, 1969, 68, 165. [all data]

Verma and Dixit, 1968
Verma, R.D.; Dixit, M.N., The D and D' states of the PO molecule, Can. J. Phys., 1968, 46, 2079. [all data]

Notes

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