Phosphorus dimer

Formula: P₂
Molecular weight: 61.947524
IUPAC Standard InChI:
InChI=1S/P2/c1-2

Download the identifier in a file.
IUPAC Standard InChIKey: FOBPTJZYDGNHLR-UHFFFAOYSA-N
CAS Registry Number: 12185-09-0
Chemical structure:
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Constants of diatomic molecules

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

Data collected through May, 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 ³¹P₂
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
Carroll and Mitchell's Rydberg series V_n converging to F ²_u⁺(v=0):
... 4_u 5_g² 2_u⁴ ns_g 1	v=125225 - R/(n-1.86)², n=5(v₅),6...16. Similar series with v'=1.
... 4_u 5_g² 2_u⁴ ns_g 1	↳Carroll and Mitchell, 1975
V₅ (¹_u⁺)	114085	[789]									V₅ X	114090
V₅ (¹_u⁺)	↳Carroll and Mitchell, 1975
... 4_u² 5_g 2_u⁴	2
... 4_u² 5_g 2_u⁴	↳missing citation
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
... 4_u² 5_g 2_u⁴ nf_u	3
... 4_u² 5_g 2_u⁴ nf_u	↳missing citation
... 4_u² 5_g 2_u⁴ nf_u	4
... 4_u² 5_g 2_u⁴ nf_u	↳missing citation
... 4_u² 5_g 2_u⁴ np_u	5
... 4_u² 5_g 2_u⁴ np_u	↳missing citation
... 4_u² 5_g 2_u⁴ np_u	6
... 4_u² 5_g 2_u⁴ np_u	↳missing citation
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
... 4_u² 5_g² 2_u³	7
... 4_u² 5_g² 2_u³	↳missing citation
... 4_u² 5_g² 2_u³ nd_g ?	8
... 4_u² 5_g² 2_u³ nd_g ?	↳missing citation
... 4_u² 5_g² 2_u³ nd_g	9
... 4_u² 5_g² 2_u³ nd_g	↳missing citation
... 4_u² 5_g² 2_u³ nd_g	10
... 4_u² 5_g² 2_u³ nd_g	↳missing citation
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
... 4_u² 5_g² 2_u³ ns_g	11
... 4_u² 5_g² 2_u³ ns_g	↳missing citation
Unclassified bands 79700 - 84500 cm^-1.
↳Carroll and Mitchell, 1975
U	83362	[551] H 12									U X R	83248 H
U	↳missing citation
G₆ (¹_u⁺)	81327	[723] 13									G₆ X R	81299 H
G₆ (¹_u⁺)	↳Creutzberg, 1966; Carroll and Mitchell, 1975
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
T	80992	[713.1] H 14									T X R	80958.5 H
T	↳Creutzberg, 1966; missing citation
S ¹_u⁺	(80840)				B₁=0.2783					r₁=1.978	S X R	81453.89 15 Z
S ¹_u⁺	↳Creutzberg, 1966; Carroll and Mitchell, 1975
R₄ (¹_u)	80115	[740] 16									R₄ X	80095
R₄ (¹_u)	↳Carroll and Mitchell, 1975
Q (¹_u)	(79860)	[617.6] H 17									Q X R	79779.5₃ H
Q (¹_u)	↳Creutzberg, 1966; Carroll and Mitchell, 1975
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
P₄ (¹_u⁺)	(79827) 18										P₄ X	79804
P₄ (¹_u⁺)	↳Carroll and Mitchell, 1975
M₄ (¹_u⁺)	(78271)	(705)	(5) 19								M₄ X R	(78233) 20
M₄ (¹_u⁺)	↳Carroll and Mitchell, 1975
H₅ (¹_u)	(78256) 21										H₅ X	78233
H₅ (¹_u)	↳Carroll and Mitchell, 1975
K₄ (¹_u)	(77968)	[732] 13									K₄ X	77944
K₄ (¹_u)	↳Carroll and Mitchell, 1975
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
O	77475	529 H	2								O X R	77349 H
O	↳missing citation
N ¹_u⁺	77286.₇	[641.76] Z	(29.7)		0.2984 22	0.0050₄		[3.1E-7]		1.909₉	N X R	77240.2₃ Z
N ¹_u⁺	↳Creutzberg, 1966; Carroll and Mitchell, 1975
L (¹_u)	73593	[672.2] H									L X R	73539.3 H
L (¹_u)	↳Creutzberg, 1966; Carroll and Mitchell, 1975
E₅ (¹_u)	73385	685 H	2.₇								E₅ X R	73337
E₅ (¹_u)	↳Carroll and Mitchell, 1975
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
M ¹_u⁺	73168.0	684.0 23 H	2.9₇		0.2802 23	0.0016				1.971	M X R	73119.6 23 H
M ¹_u⁺	↳Creutzberg, 1966; Carroll and Mitchell, 1975
K ¹_u	72288	[701.7] H^Q	(5)		[0.2704] 24 22					[2.006]	K X R	72253.3 Z
K ¹_u	↳Creutzberg, 1966; Carroll and Mitchell, 1975
Numerous diffuse irregularly spaced "lines" 69900 - 70400 cm^-1, no assignments.
↳Creutzberg, 1966
H (¹_u)	(68960) 25										H X	68940
H (¹_u)	↳Creutzberg, 1966; Carroll and Mitchell, 1975
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
I ¹_u	[68849.3]				[0.2541]			[2.₅E-7]		[2.070]	I X R	68459.6₃ Z
I ¹_u	↳Creutzberg, 1966
G ¹_u⁺	66313.37	694.12 Z	4.18₂		0.29730 22	0.00195		[2.25E-7]		1.9135	G X R	66269.71 Z
G ¹_u⁺	↳Dressler, 1955; missing citation
E ¹_u	59446.21	700.66 H^Q	2.92		[0.2807₂] 22			[1.84E-7]		[1.969₂]	E X 26 R	59406.14 Z
E ¹_u	↳Dressler, 1955; missing citation
B ¹_u	50845.9	[358.96] 27 Z	28		[0.2268] 27	29		[3.2E-7]		[2.191]	B A R	16203.7₁ 27 Z
B ¹_u	↳Malicet, Brion, et al., 1973; missing citation
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
c ³_u2	47176.8	393.67 Z	3.849 30	-.0915	0.2190 31	0.0024		2.5E-7		2.229	c b 32 R	18721.5 Z
c ³_u2	↳Brion, da Paz, et al., 1971; missing citation; Carroll and Nulty, 1976; missing citation
c ³_u1	47159.1	393.67 Z	3.849 30	-.0915	0.2190 31	0.0024		2.5E-7		2.229	c b 32 R	18836.4 Z
c ³_u1	↳Brion, da Paz, et al., 1971; missing citation; Carroll and Nulty, 1976; missing citation
c ³_u0	47139.2	393.67 Z	3.849 30	-.0915	0.2190 31	0.0024		2.5E-7		2.229	c b 32 R	18944.6 Z
c ³_u0	↳Brion, da Paz, et al., 1971; missing citation; Carroll and Nulty, 1976; missing citation
C ¹_u⁺	46941.26	473.93 Z	2.340 33	0.0066	0.24211 34 22	0.00175	3.₃E-6	2.57E-7		2.1204	C X R	46787.97 Z
C ¹_u⁺	↳missing citation; missing citation; Marais and Verleger, 1950; Creutzberg, 1966; missing citation; missing citation
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
A ¹_g	34515.25	618.95 Z	3.00		0.27524	0.00168		2.2E-7		1.9887	A X R	34434.30 Z
A ¹_g	↳missing citation; Verma and Broida, 1970; Malicet, Brion, et al., 1973; missing citation
b ²_g2	28329.6	644.66 Z	3.213 35		0.2805	0.00178		2.0E-7		1.970	b a 32 V	9574.8 Z
b ²_g2	↳Mrozowski and Santaram, 1967; Brion and Malicet, 1975; missing citation; Carroll and Nulty, 1976
b ²_g1	28197.0	644.66 Z	3.213 35		0.2805	0.00178		2.0E-7		1.970	b a 32 V	9442.2 Z
b ²_g1	↳Mrozowski and Santaram, 1967; Brion and Malicet, 1975; missing citation; Carroll and Nulty, 1976
b ²_g0	28068.9	644.66 Z	3.213 35		0.2805	0.00178		2.0E-7		1.970	b a 32 V	9314.1 Z
b ²_g0	↳Mrozowski and Santaram, 1967; Brion and Malicet, 1975; missing citation; Carroll and Nulty, 1976
State	T_e	_e	_ex_e	_ey_e	B_e	_e	_e	D_e	_e	r_e	Trans.	₀₀
b' ³_u^-	28503.4 36	604.4₈ Z	2.2		0.2584 37	0.0014		1.7E-7		2.052	b' X R	28415.4 Z
b' ³_u^-	↳Mrozowski and Santaram, 1967; missing citation
a ³⁺	18794.5	565.1₇ H	2.7₅		B₁=0.2503₃ 38			D₁=3.3E-7		r₁=2.085₃	(a-X)	18686.7 39
X ¹_g⁺	0	780.77 Z	2.83₅ 40	-0.00462	0.30362 22	0.00149 41	-2.7E-6	1.88E-7		1.8934

Notes

Core configuration as suggested by Bulgin, Dyke, et al., 1976 on the basis of ab initio calculations; Carroll and Mitchell Carroll and Mitchell, 1975 proposed... 4 sigma

_u² 5

_g 2

_u³ 2

_g.

Carrol and Mitchel's Rydberg series G_n, H_n, P_n, R_n converging to A ² Sigma

_g⁺(v=0):

v=87179 - R/(n-0.062-0.633/n*²)², n=4(R₄),5...21.

v=87179 - R/(n-0.155-0.179/n*²)², n=4(P₄),5...14.

v=87179 - R/(n-1.468-0.475/n*²)², n=4(H),5(H₅),6...28.

v=87179 - R/(n-1.660-0.252/n*²)², n=4(G),5(N),6(G₆),7...12.

Carrol and Mitchel's Rydberg series E_n, K_n, M_n, L_n converging to X₂ ²

_1/2(v=1):

v~85895 - R/(n+0.04)², n=3(L),4. Fragments of series with v'=0 (V =85229) and with v'>1.

v~85895 - R/(n+0.03)², n=3(M),4(M₄),5(S). Fragments of series with v'=0 (V =85229) and with v'>1.

v~85895 - R/(n+0.12)², n=3(K),4...10. Fragments of series with v'=0 (V =85229) and with v'>1.

v~85895 - R/(n+1.93)², n=4(E),5(E₅),6. Fragments of series with v'=0 (V =85229) and with v'>1.

Observed to v'=2.

Diffuse bands.

Observed to v'=4.

Assigned as 0-0 band by Creutzberg, 1966; reassigned as 1-0 band by Carroll and Mitchell, 1975 [third member of the M_n(v'=1) Rydberg series].

Broad diffuse bands.

0-0 and 1-1 bands only.

Broad band.

Only v'=1 and 3 (diffuse) observed.

0-0 band obscured by H₅ larrow

X 0-0.

Very broad band.

RKR potential functions Singh and Rai, 1966, Rao and Lakshman, 1970.

Following Carroll and Mitchell, 1975 the v' numbering of Creutzberg, 1966 has been increased by one unit.

All lines of this system are diffuse; the diffuseness is largest for v'=3 and 4 such that the rotational structure can no longer be recognized. The broadening is independent of J; the state causing the predissociation is probably ¹

_u.

Very intense diffuse band, width ~80 cm^-1.

Franck-Condon factors Rao and Lakshman, 1970.

The assignment of v'=0 to the lowest observed level is arbitrary.

G(3/2) = 352.71.

B₁ = 0.2209, B₂ = 0.217₁.

Carroll and Nulty, 1976; slightly different constants in missing citation.

Perturbations by C ¹ Sigma

_u⁺. The observation of extra lines enables the relative position of singlet and triplet levels to be determined Carroll and Nulty, 1976; very similar results have been obtained by Brion, Malicet, et al., 1976, missing citation.

Franck-Condon factors Brion and Malicet, 1976.

Constants from Creutzberg, 1966, but see missing citation whose deperturbation of the C state levels (see 34) leads to T_e = 46945.5₇, omega

_e = 472.81, omega

_ex_e = 2.24₆, omega

_ey_e = +0.00412₂.

Strong vibrational perturbations for v=1,2,3,5 Herzberg, 1932 and many rotational perturbations Marais, 1946, Marais and Verleger, 1950, Naude and Verleger, 1950, Creutzberg, 1966, Brion, Malicet, et al., 1976, 2 due to interaction with levels of c ³

_u see missing citation. Breaking off in emission (predissociation) above J=58 of v=10 and J=34 of v=11; the corresponding dissociation limit is ⁴S + ²D at 51959 ± 25 cm^-1. A second predissociation indicated by diffuseness in absorption begins at v=17 and reaches a maximum for low J values of v=19 Creutzberg, 1966.

_ey_e < 0.001 cm^-1 Carroll and Nulty, 1976; slightly different constants in missing citation.

Recalculated; Brion, Malicet, et al., 1974 give 28507.74 which probably refers to data obtained from band heads rather than band origins.

Spin splitting constants lambda

= +3.20,

= -0.001.

Spin splitting constants lambda

₁= -3.2₁,

₁= -0.003 Brion and Malicet, 1976.

Not observed; indirectly derived Carroll and Nulty, 1976 from perturbations in c ³

_u; see 31.

missing citation; slightly different constants in Marais and Verleger, 1950 and Creutzberg, 1966.

Constants recalculated from the data of Herzberg, 1932, Douglas and Rao, 1958, Creutzberg, 1966, Dixit, 1968. Higher B_v values not included in the reevaluation may be found in Herzberg, 1932, Marais and Verleger, 1950.

From the predissociation limit in C ¹ Sigma

_u+ which according to Herzberg, 1932 is equal to the dissociation limit ⁴S+²D. The latest thermochemical (mass-spectrometric) value is 5.04 eV Kordis and Gingerich, 1973 eliminating the possibility that the predissociation limit corresponds to ²D+²D as suggested by Vaidyan and Santaram, 1971.

From the photoelectron spectrum Bulgin, Dyke, et al., 1976 which shows partially resolved peaks at 10.53 and 10.55 eV corresponding to X₁ ²

_3/2 and X₂ ²

_1/2, respectively. Subtraction of the estimated doublet splitting in the X ²

ground state [~ 260 cm^-1, see ref. 6 of P₂⁺] from the Rydberg series limit at 85229 cm^-1 Carroll and Mitchell, 1975 gives l0.53₅ eV.

References

Go To: Top, Constants of diatomic molecules, Notes

Carroll and Mitchell, 1975
Carroll, P.K.; Mitchell, P.I., The absorption spectrum of diatomic phosphorus between 1370 and 600 A, Proc. Roy. Soc. London A, 1975, 342, 93. [all data]

Creutzberg, 1966
Creutzberg, F., The absorption spectrum of the P₂ molecule in the vacuum ultraviolet, Can. J. Phys., 1966, 44, 1583. [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]

Malicet, Brion, et al., 1973
Malicet, J.; Brion, J.; Guenebaut, H., Analyse de quatre bandes d'une nouvelle transition ¹«PI»-¹«PI» du radical P₂, C.R. Acad. Sci. Paris, Ser. C, 1973, 276, 991. [all data]

Brion, da Paz, et al., 1971
Brion, J.; da Paz, M.; Mongin, J.; Guenebaut, H., Analyse rotationnelle de quatre nouvelles bandes d'un systeme electronique visible du radical P₂, C.R. Acad. Sci. Paris, Ser. B, 1971, 272, 999-1002. [all data]

Carroll and Nulty, 1976
Carroll, P.K.; Nulty, A.T., Rotational analysis of the visible system of P₂ and the location of the triplet states, J. Phys. B:, 1976, 9, 427. [all data]

Marais and Verleger, 1950
Marais, E.J.; Verleger, H., The rotational structure of the ultraviolet band system of the P₂ molecule, Phys. Rev., 1950, 80, 429. [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]

Mrozowski and Santaram, 1967
Mrozowski, S.; Santaram, C., Electronic spectra of P₂, As₂, and Sb₂ molecules, J. Opt. Soc. Am., 1967, 57, 522. [all data]

Brion and Malicet, 1975
Brion, J.; Malicet, J., Nouvelle transition du radical P₂ analogue au premier systeme positif de l'azote, J. Phys. B:, 1975, 8, 164. [all data]

Bulgin, Dyke, et al., 1976
Bulgin, D.K.; Dyke, J.M.; Morris, A., HeI photoelectron spectrum of the P₂(X¹«SIGMA»⁺₎ molecule, J. Chem. Soc. Faraday Trans. 2, 1976, 72, 2225. [all data]

Singh and Rai, 1966
Singh, R.B.; Rai, D.K., Potential curves for some diatomic molecules: P₂, PN, SiN, NBr, BaO, BeF, SiF & SnF, Indian J. Pure Appl. Phys., 1966, 4, 102. [all data]

Rao and Lakshman, 1970
Rao, T.V.R.; Lakshman, S.V.J., Potential energy curves, r-centroids & Franck-Condon factors for the bands of P₂ molecule, Indian J. Pure Appl. Phys., 1970, 8, 617. [all data]

Brion, Malicet, et al., 1976
Brion, J.; Malicet, J.; France, M.; Lafore, M., Peturbations dans les etats C¹«SIGMA»_u⁺ et c³«PI»_u du radical P₂, C.R. Acad. Sci. Paris, Ser. C, 1976, 283, 171. [all data]

Brion and Malicet, 1976
Brion, J.; Malicet, J., Spectre d'emission du radical P₂: transitions c³«PI»_u-b³«PI»_g et b³«PI»_g-a³«SIGMA»_u⁺, J. Phys. B:, 1976, 9, 2097. [all data]

Herzberg, 1932
Herzberg, G., Bandenspektrum, pradissoziation und struktur des P₂-molekuls, Ann. Phys. (Leipzig), 1932, 15, 677. [all data]

Marais, 1946
Marais, E.J., Perturbations in the ultraviolet band spectrum of P₂, Phys. Rev., 1946, 70, 499. [all data]

Naude and Verleger, 1950
Naude, S.M.; Verleger, H., The perturbations in the ultraviolet band spectrum of the phosphorus molecule P₂, Phys. Rev., 1950, 80, 432. [all data]

Brion, Malicet, et al., 1976, 2
Brion, J.; Malicet, J.; Guenebaut, H., Spectre d'emission du radical P₂: etude des transitions C¹«SIGMA»_u⁺-X¹«SIGMA»_g⁺, A¹«PI»_g-X¹«SIGMA»_g⁺ et B¹«PI»_u-A¹«PI»_g, Can. J. Phys., 1976, 54, 362. [all data]

Brion, Malicet, et al., 1974
Brion, J.; Malicet, J.; Guenebaut, H., Spectre d'emission du radical P₂: etude de la transition b'³«SIGMA»_u^- - X¹«SIGMA»_g⁺, Can. J. Phys., 1974, 52, 2143-2149. [all data]

Douglas and Rao, 1958
Douglas, A.E.; Rao, K.S., A new band system of the P₂ molecule analogous to the Lyman-Birge-Hopfield bands of N₂, Can. J. Phys., 1958, 36, 565. [all data]

Dixit, 1968
Dixit, M.N., Rotational analysis of some bands of C¹«SIGMA»_u⁺-X¹«SIGMA»_g⁺ system of P₂ molecule involving low v', v" values, Proc. Indian Acad. Sci. Sect. A, 1968, 66, 325. [all data]

Kordis and Gingerich, 1973
Kordis, J.; Gingerich, K.A., Mass spectroscopic investigation of the equilibrium dissociation of gaseous Sb₂, Sb₃, Sb₄, SbP, SbP₃, and P₂, J. Chem. Phys., 1973, 58, 5141. [all data]

Vaidyan and Santaram, 1971
Vaidyan, V.K.; Santaram, C., Dissociation energy & potential energy curves of P₂, Indian J. Pure Appl. Phys., 1971, 9, 1022. [all data]

Notes

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Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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