Home Symbol which looks like a small house Up Solid circle with an upward pointer in it

Phosphorus dimer


Constants of diatomic molecules

Go To: Top, 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: Klaus P. Huber and Gerhard H. Herzberg

Data collected through May, 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 31P2
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
Carroll and Mitchell's Rydberg series Vn converging to F 2Sigmau+(v=0):
... 4sigmau 5sigmag2 2piu4 nssigmag 1v=125225 - R/(n-1.86)2, n=5(v5),6...16. Similar series with v'=1.
Carroll and Mitchell, 1975
V5 (1Sigmau+) 114085 [789]         V5 larrow X 114090
Carroll and Mitchell, 1975
... 4sigmau2 5sigmag 2piu4 2           
missing citation
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
... 4sigmau2 5sigmag 2piu4 nfpiu 3           
missing citation
... 4sigmau2 5sigmag 2piu4 nfsigmau 4           
missing citation
... 4sigmau2 5sigmag 2piu4 nppiu 5           
missing citation
... 4sigmau2 5sigmag 2piu4 npsigmau 6           
missing citation
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
... 4sigmau2 5sigmag2 2piu3 7           
missing citation
... 4sigmau2 5sigmag2 2piu3 nddeltag ? 8           
missing citation
... 4sigmau2 5sigmag2 2piu3 ndpig 9           
missing citation
... 4sigmau2 5sigmag2 2piu3 ndsigmag 10           
missing citation
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
... 4sigmau2 5sigmag2 2piu3 nssigmag 11           
missing citation
Unclassified bands 79700 - 84500 cm-1.
Carroll and Mitchell, 1975
U 83362 [551] H 12         U larrow X R 83248 H
missing citation
G6 (1Sigmau+) 81327 [723] 13         G6 larrow X R 81299 H
Creutzberg, 1966; Carroll and Mitchell, 1975
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
T 80992 [713.1] H 14         T larrow X R 80958.5 H
Creutzberg, 1966; missing citation
S 1Sigmau+ (80840)    B1=0.2783     r1=1.978 S larrow X R 81453.89 15 Z
Creutzberg, 1966; Carroll and Mitchell, 1975
R4 (1Piu) 80115 [740] 16         R4 larrow X 80095
Carroll and Mitchell, 1975
Q (1Piu) (79860) [617.6] H 17         Q larrow X R 79779.53 H
Creutzberg, 1966; Carroll and Mitchell, 1975
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
P4 (1Sigmau+) (79827) 18          P4 larrow X 79804
Carroll and Mitchell, 1975
M4 (1Sigmau+) (78271) (705) (5) 19        M4 larrow X R (78233) 20
Carroll and Mitchell, 1975
H5 (1Piu) (78256) 21          H5 larrow X 78233
Carroll and Mitchell, 1975
K4 (1Piu) (77968) [732] 13         K4 larrow X 77944
Carroll and Mitchell, 1975
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
O 77475 529 H 2        O larrow X R 77349 H
missing citation
N 1Sigmau+ 77286.7 [641.76] Z (29.7)  0.2984 22 0.00504  [3.1E-7]  1.9099 N larrow X R 77240.23 Z
Creutzberg, 1966; Carroll and Mitchell, 1975
L (1Piu) 73593 [672.2] H         L larrow X R 73539.3 H
Creutzberg, 1966; Carroll and Mitchell, 1975
E5 (1Piu) 73385 685 H 2.7        E5 larrow X R 73337
Carroll and Mitchell, 1975
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
M 1Sigmau+ 73168.0 684.0 23 H 2.97  0.2802 23 0.0016    1.971 M larrow X R 73119.6 23 H
Creutzberg, 1966; Carroll and Mitchell, 1975
K 1Piu 72288 [701.7] HQ (5)  [0.2704] 24 22     [2.006] K larrow X R 72253.3 Z
Creutzberg, 1966; Carroll and Mitchell, 1975
Numerous diffuse irregularly spaced "lines" 69900 - 70400 cm-1, no assignments.
Creutzberg, 1966
H (1Piu) (68960) 25          H larrow X 68940
Creutzberg, 1966; Carroll and Mitchell, 1975
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
I 1Piu [68849.3]    [0.2541]   [2.5E-7]  [2.070] I larrow X R 68459.63 Z
Creutzberg, 1966
G 1Sigmau+ 66313.37 694.12 Z 4.182  0.29730 22 0.00195  [2.25E-7]  1.9135 G lrarrow X R 66269.71 Z
Dressler, 1955; missing citation
E 1Piu 59446.21 700.66 HQ 2.92  [0.28072] 22   [1.84E-7]  [1.9692] E lrarrow X 26 R 59406.14 Z
Dressler, 1955; missing citation
B 1Piu 50845.9 [358.96] 27 Z 28  [0.2268] 27 29  [3.2E-7]  [2.191] B rarrow A R 16203.71 27 Z
Malicet, Brion, et al., 1973; missing citation
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
c 3Piu2 47176.8 393.67 Z 3.849 30 -.0915 0.2190 31 0.0024  2.5E-7  2.229 c rarrow b 32 R 18721.5 Z
Brion, da Paz, et al., 1971; missing citation; Carroll and Nulty, 1976; missing citation
c 3Piu1 47159.1 393.67 Z 3.849 30 -.0915 0.2190 31 0.0024  2.5E-7  2.229 c rarrow b 32 R 18836.4 Z
Brion, da Paz, et al., 1971; missing citation; Carroll and Nulty, 1976; missing citation
c 3Piu0 47139.2 393.67 Z 3.849 30 -.0915 0.2190 31 0.0024  2.5E-7  2.229 c rarrow b 32 R 18944.6 Z
Brion, da Paz, et al., 1971; missing citation; Carroll and Nulty, 1976; missing citation
C 1Sigmau+ 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 lrarrow X R 46787.97 Z
missing citation; missing citation; Marais and Verleger, 1950; Creutzberg, 1966; missing citation; missing citation
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
A 1Pig 34515.25 618.95 Z 3.00  0.27524 0.00168  2.2E-7  1.9887 A rarrow X R 34434.30 Z
missing citation; Verma and Broida, 1970; Malicet, Brion, et al., 1973; missing citation
b 2Pig2 28329.6 644.66 Z 3.213 35  0.2805 0.00178  2.0E-7  1.970 b rarrow a 32 V 9574.8 Z
Mrozowski and Santaram, 1967; Brion and Malicet, 1975; missing citation; Carroll and Nulty, 1976
b 2Pig1 28197.0 644.66 Z 3.213 35  0.2805 0.00178  2.0E-7  1.970 b rarrow a 32 V 9442.2 Z
Mrozowski and Santaram, 1967; Brion and Malicet, 1975; missing citation; Carroll and Nulty, 1976
b 2Pig0 28068.9 644.66 Z 3.213 35  0.2805 0.00178  2.0E-7  1.970 b rarrow a 32 V 9314.1 Z
Mrozowski and Santaram, 1967; Brion and Malicet, 1975; missing citation; Carroll and Nulty, 1976
StateTeomegaeomegaexeomegaeyeBealphaegammaeDebetaereTrans.nu00
b' 3Sigmau- 28503.4 36 604.48 Z 2.2  0.2584 37 0.0014  1.7E-7  2.052 b' rarrow X R 28415.4 Z
Mrozowski and Santaram, 1967; missing citation
a 3Sigma+ 18794.5 565.17 H 2.75  B1=0.25033 38   D1=3.3E-7  r1=2.0853 (a-X) 18686.7 39
X 1Sigmag+ 0 780.77 Z 2.835 40 -0.00462 0.30362 22 0.00149 41 -2.7E-6 1.88E-7  1.8934  

Notes

1Core configuration as suggested by Bulgin, Dyke, et al., 1976 on the basis of ab initio calculations; Carroll and Mitchell Carroll and Mitchell, 1975 proposed... 4sigmau2 5sigmag 2piu3 2pig.
2Carrol and Mitchel's Rydberg series Gn, Hn, Pn, Rn converging to A 2Sigmag+(v=0):
3v=87179 - R/(n-0.062-0.633/n*2)2, n=4(R4),5...21.
4v=87179 - R/(n-0.155-0.179/n*2)2, n=4(P4),5...14.
5v=87179 - R/(n-1.468-0.475/n*2)2, n=4(H),5(H5),6...28.
6v=87179 - R/(n-1.660-0.252/n*2)2, n=4(G),5(N),6(G6),7...12.
7Carrol and Mitchel's Rydberg series En, Kn, Mn, Ln converging to X2 2Pi1/2(v=1):
8v~85895 - R/(n+0.04)2, n=3(L),4. Fragments of series with v'=0 (V =85229) and with v'>1.
9v~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.
10v~85895 - R/(n+0.12)2, n=3(K),4...10. Fragments of series with v'=0 (V =85229) and with v'>1.
11v~85895 - R/(n+1.93)2, n=4(E),5(E5),6. Fragments of series with v'=0 (V =85229) and with v'>1.
12Observed to v'=2.
13Diffuse bands.
14Observed to v'=4.
15Assigned as 0-0 band by Creutzberg, 1966; reassigned as 1-0 band by Carroll and Mitchell, 1975 [third member of the Mn(v'=1) Rydberg series].
16Broad diffuse bands.
170-0 and 1-1 bands only.
18Broad band.
19Only v'=1 and 3 (diffuse) observed.
200-0 band obscured by H5larrow X 0-0.
21Very broad band.
22RKR potential functions Singh and Rai, 1966, Rao and Lakshman, 1970.
23Following Carroll and Mitchell, 1975 the v' numbering of Creutzberg, 1966 has been increased by one unit.
24All 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 1Piu.
25Very intense diffuse band, width ~80 cm-1.
26Franck-Condon factors Rao and Lakshman, 1970.
27The assignment of v'=0 to the lowest observed level is arbitrary.
28DeltaG(3/2) = 352.71.
29B1 = 0.2209, B2 = 0.2171.
30 Carroll and Nulty, 1976; slightly different constants in missing citation.
31Perturbations by C 1Sigmau+. 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.
32Franck-Condon factors Brion and Malicet, 1976.
33Constants from Creutzberg, 1966, but see missing citation whose deperturbation of the C state levels (see 34) leads to Te = 46945.57, omegae = 472.81, omegaexe = 2.246, omegaeye = +0.004122.
34Strong 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 3Piu 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.
35omegaeye < 0.001 cm-1 Carroll and Nulty, 1976; slightly different constants in missing citation.
36Recalculated; Brion, Malicet, et al., 1974 give 28507.74 which probably refers to data obtained from band heads rather than band origins.
37Spin splitting constants lambda = +3.20, gamma = -0.001.
38Spin splitting constants lambda1= -3.21, gamma1= -0.003 Brion and Malicet, 1976.
39Not observed; indirectly derived Carroll and Nulty, 1976 from perturbations in c 3Piu; see 31.
40 missing citation; slightly different constants in Marais and Verleger, 1950 and Creutzberg, 1966.
41Constants recalculated from the data of Herzberg, 1932, Douglas and Rao, 1958, Creutzberg, 1966, Dixit, 1968. Higher Bv values not included in the reevaluation may be found in Herzberg, 1932, Marais and Verleger, 1950.
42From the predissociation limit in C 1Sigmau+ 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.
43From the photoelectron spectrum Bulgin, Dyke, et al., 1976 which shows partially resolved peaks at 10.53 and 10.55 eV corresponding to X1 2Pi3/2 and X2 2Pi1/2, respectively. Subtraction of the estimated doublet splitting in the X 2Pi 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

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

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

Go To: Top, Constants of diatomic molecules, References