Phosphinidene

Formula: HP
Molecular weight: 31.98170
IUPAC Standard InChI: InChI=1S/HP/h1H
IUPAC Standard InChIKey: BHEPBYXIRTUNPN-UHFFFAOYSA-N
CAS Registry Number: 13967-14-1
Chemical structure:
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Gas phase ion energetics data

Go To: Top, Constants of diatomic molecules, References, Notes

Data evaluated as indicated in comments:
HL - Edward P. Hunter and Sharon G. Lias

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

View reactions leading to HP⁺ (ion structure unspecified)

Quantity	Value	Units	Method	Reference	Comment
Proton affinity (review)	670.3	kJ/mol	N/A	Hunter and Lias, 1998	HL
Quantity	Value	Units	Method	Reference	Comment
Gas basicity	639.6	kJ/mol	N/A	Hunter and Lias, 1998	HL

Electron affinity determinations

EA (eV)	Method	Reference	Comment
1.0270 ± 0.0060	LPES	Ervin and Lineberger, 2005	B
1.028 ± 0.010	LPES	Zittel and Lineberger, 1976	B
1.00 ± 0.060	PD	Rackwitz, Feldman, et al., 1977	B
>0.50 ± 0.20	EIAE	Halmann and Platzner, 1969	From PH₃; B
<1.09997	IMRB	Ebinghaus, Kraus, et al., 1964	B

Ionization energy determinations

IE (eV)	Method	Reference	Comment
10.149 ± 0.008	PI	Berkowitz and Cho, 1988	LL
10.2 ± 0.1	DER	Berkowitz, Curtiss, et al., 1986	LBLHLM

De-protonation reactions

P^- + = Phosphinidene

By formula: P^- + H⁺ = HP

Quantity	Value	Units	Method	Reference	Comment
Δ_rH°	1538. ± 33.	kJ/mol	D-EA	Andersson, Lindahl, et al., 2007	gas phase; B
Quantity	Value	Units	Method	Reference	Comment
Δ_rG°	1515. ± 34.	kJ/mol	H-TS	Andersson, Lindahl, et al., 2007	gas phase; B

Constants of diatomic molecules

Go To: Top, Gas phase ion energetics data, References, Notes

Data compiled by: Klaus P. Huber and Gerhard H. Herzberg

Data collected through July, 1977

Symbols used in the table of constants
Symbol	Meaning
State	electronic state and / or symmetry symbol
T_e	minimum electronic energy (cm^-1)
ω_e	vibrational constant – first term (cm^-1)
ω_ex_e	vibrational constant – second term (cm^-1)
ω_ey_e	vibrational constant – third term (cm^-1)
B_e	rotational constant in equilibrium position (cm^-1)
α_e	rotational constant – first term (cm^-1)
γ_e	rotation-vibration interaction constant (cm^-1)
D_e	centrifugal distortion constant (cm^-1)
β_e	rotational constant – first term, centrifugal force (cm^-1)
r_e	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
State	T_e	ω_e	ω_ex_e	ω_ey_e	B_e	α_e	γ_e	D_e	β_e	r_e	Trans.	ν₀₀
d ¹Π					[8.47₈] 1			[4.1₇E-4]		[1.427₃]	d ← a	62725.28 Z
d ¹Π	↳missing citation
B ³Π₀					[7.3]					[1.5₄]	B ← X R	69587.8 Z
B ³Π₀	↳Balfour and Douglas, 1968
c ¹Φ					[8.60₂]	0.21		[5.4₄E-4]		[1.417₀]	c ← a 2	61548.6₈ Z
c ¹Φ	↳missing citation
A ³Π_i,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
A ³Π_i,0+	↳missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
State	T_e	ω_e	ω_ex_e	ω_ey_e	B_e	α_e	γ_e	D_e	β_e	r_e	Trans.	ν₀₀
A ³Π_i,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
A ³Π_i,0-	↳missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
A ³Π_i,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
A ³Π_i,1	↳missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
A ³Π_i,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
A ³Π_i,2	↳missing citation; missing citation; missing citation; Horani, Rostas, et al., 1967; Rostas, Cossart, et al., 1974
b ¹Σ⁺	(15160) 10
State	T_e	ω_e	ω_ex_e	ω_ey_e	B_e	α_e	γ_e	D_e	β_e	r_e	Trans.	ν₀₀
a ¹Δ	(7660) 10				[8.443]	0.12		[4.1₈E-4]		[1.4302] 11
a ¹Δ	↳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
X ³Σ^-	↳Davies, Russell, et al., 1975

Notes

Λ-type doubling |Δv| = 0.1275J(J+l) - 0.54E-4J²(J+1)².

Sequence of nearly undegraded bands; the origins of the 1-1 and 2-2 bands are at 61554.5 and 61560.7 cm^-1, respectively.

A₀ = -115.71, A₁ = -115.20; see Rostas, Cossart, et al., 1974 who give also centrifugal distortion corrections A_D as well as estimated spin-spin and second-order spin-orbit parameters.

Estimated using isotope relations.

For Λ-doubling constants see Rostas, Cossart, et al., 1974.

B₁ = 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.

D₁ = 6.54E-4, H₀ = -1.6E-8.

Lifetime τ= 0.45 μs, corresponding to an absorption oscillator strength of 0.0078 Fink and Welge, 1964.

Subband origins as defined by Rostas, Cossart, et al., 1974.

Theoretical 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^-).

Rotation sp. 15

Constants deduced from isotope relations Rostas, Cossart, et al., 1974.

Spin splitting constants λ₀ = +2.21₂, γ₀ = -0.073₈; λ₁ = +2.20₇, γ₁ = -0.072₆ Rostas, Cossart, et al., 1974.

Adjusted theoretical value recommended by Meyer and Rosmus, 1975; see also Jordan, 1964, Cade and Huo, 1967, Liu, Legentil, et al., 1972.

N=4→5 rotational transitions observed by the laser magnetic resonance method.

From the value for PH.

A₀= -115.74, A₁= -115.55; see also 3.

B₁= 4.0047.

D₁= 1.640E-4.

Spin splitting constants λ₀= +2.211, γ₀= -0.0385; λ₁= +2.20₂, γ₁= 0.038₁ Rostas, Cossart, et al., 1974.

References

Go To: Top, Gas phase ion energetics data, Constants of diatomic molecules, Notes

Hunter and Lias, 1998
Hunter, E.P.; Lias, S.G., Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update, J. Phys. Chem. Ref. Data, 1998, 27, 3, 413-656, https://doi.org/10.1063/1.556018 . [all data]

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]

Zittel and Lineberger, 1976
Zittel, P.F.; Lineberger, W.C., Laser photoelectron spectrometry of PO-, PH-, and PH₂-, J. Chem. Phys., 1976, 65, 1236. [all data]

Rackwitz, Feldman, et al., 1977
Rackwitz, R.; Feldman, D.; Kaiser, H.J.; Heincke, E., Photodetachment bei einigen zweiatomigen negativen hydridionen: BeH-, MgH-, CaH-, ZnH-, PH-, AsH-, Z. Naturforsch. A:, 1977, 32, 594. [all data]

Halmann and Platzner, 1969
Halmann, M.; Platzner, I., Negative Ions Produced by Electron Capture in Phosphine, J. Phys. Chem., 1969, 73, 12, 4376, https://doi.org/10.1021/j100846a062 . [all data]

Ebinghaus, Kraus, et al., 1964
Ebinghaus, H.; Kraus, K.; Neuert, H.; Muller-Duysing, W., Negative Ionen durch Elecktronenresonanzeinfang in PH₃, AsH₃, und SiH₄, Z. Naturfor., 1964, 19A, 732. [all data]

Berkowitz and Cho, 1988
Berkowitz, J.; Cho, H., A photoionization study of PH: PH₂ revisited, J. Chem. Phys., 1988, 90, 1. [all data]

Berkowitz, Curtiss, et al., 1986
Berkowitz, J.; Curtiss, L.; Gibson, S.; Greene, J.; Hillhouse, G.; Pople, J., Photoionization mass spectrometric study and Ab initio calculation of ionization and bonding in P-H compounds. Heats of formation, bond energies, and the 3B₁-1A1 separation in PH₂⁺, J. Chem. Phys., 1986, 84, 375. [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 A³Π_i-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(C³Π_u), N₂⁺(B²Σ_u⁺), 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

Go To: Top, Gas phase ion energetics data, Constants of diatomic molecules, References

Symbols used in this document:

EA Electron affinity

Δ_rG° Free energy of reaction at standard conditions

Δ_rH° Enthalpy of reaction at standard conditions
Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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EA	Electron affinity
Δ_rG°	Free energy of reaction at standard conditions
Δ_rH°	Enthalpy of reaction at standard conditions