Sulfur dimer

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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 32S2
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
Additional progressions and unassigned bands in the absorption spectrum 65700 - 71900 cm-1.
↳Mahajan, Lakshminarayana, et al., 1976
F 2 (66333) [827] 1 H         F ← X 66384 1 H
↳Donovan, Husain, et al., 1970; Mahajan, Lakshminarayana, et al., 1976
(66229) [827] 1 H         F ← X 66280 1 H
↳Donovan, Husain, et al., 1970; Mahajan, Lakshminarayana, et al., 1976
E 2 (65933) [818] 1 H         E ← X 65980 1 H
↳Donovan, Husain, et al., 1970; Mahajan, Lakshminarayana, et al., 1976
(65829) [818] 1 H         E ← X 65876 1 H
↳Donovan, Husain, et al., 1970; Mahajan, Lakshminarayana, et al., 1976
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
j 3          j → (b) 4 V 56077.7 H
↳missing citation
i  [785.0] H         i → (b) 4 V 55099.3 H
↳missing citation
h  819.6 H 2.70        h → (b) 4 V 51461.4 H
↳missing citation
D 3Πu,r 58978.7 793.8 H 4.00  [0.3073]   [1.85E-7]  [1.8546] D ↔ X V 59012.50 Z
↳missing citation; Tanaka and Ogawa, 1962; Ricks and Barrow, 1969
58691.7 793.8 H 4.00  [0.3066]   [1.85E-7]  [1.8546] D ↔ X V 58725.47 Z
↳missing citation; Tanaka and Ogawa, 1962; Ricks and Barrow, 1969
58518.3 793.8 H 4.00  [0.3059]   [1.85E-7]  [1.8546] D ↔ X V 58552.05 Z
↳missing citation; Tanaka and Ogawa, 1962; Ricks and Barrow, 1969
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
g 1Δu x+ 52187.7 816.0 H 2.70  [0.3210]   (2.0E-7)  [1.8125] g ↔ a 5 V 52244.66 Z
↳missing citation; Barrow and Du Parcq, 1968
C' (3Σu-) 6          C' → X V 56621.6 H
↳missing citation
C 3Σu- 55581.7 829.15 Z 3.34  0.3219 7 0.00138 -2.3E-4 [2.17E-7]  1.8100 C ↔ X V 55633.3 8 Z
↳Wieland, Wehrli, et al., 1934; missing citation; Tanaka and Ogawa, 1962; missing citation
f 1Δu x+ 36875.45 438.32 Z 2.70 -0.005 0.22704 9 0.00178  (2.43E-7)  2.1551 f ↔ a 10 R 36743.53 Z
↳Barrow and Du Parcq, 1968; Carleer and Colin, 1970
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
B' 3Πg,i     11      B' → A V 
↳Narasimham, 1964; Narasimham and Apparao, 1966; missing citation
z+ (14504) [533.7] 12 (Z)   [0.2441] 11     [2.078] B' → A V 13451.95 13 Z
↳Narasimham, 1964; Narasimham and Apparao, 1966; missing citation
z+ (14295)    [0.2435] 11      B' → A V 13320.64 13 Z
↳Narasimham, 1964; Narasimham and Apparao, 1966; missing citation
           B' → A' V 
↳Meakin and Barrow, 1962; Narasimham, 1964; Narasimham and Apparao, 1966; missing citation
           B' → A' V 14144.37 Z
↳Meakin and Barrow, 1962; Narasimham, 1964; Narasimham and Apparao, 1966; missing citation
           B' → A' V 14318.07 Z
↳Meakin and Barrow, 1962; Narasimham, 1964; Narasimham and Apparao, 1966; missing citation
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
B 3Σu- 31835 434.0 14 2.75 14  0.2239 14 15 16 0.0023 14  [2.4E-7] 14  2.170 B ↔ X 17 18 R 31689 19
↳Olsson, 1938; Ikenoue, 1960; Barrow and du Parcq, 1965
A 3Σu+(0u-) z+ 1078 20 482.75 Z 2.58  0.2301 0.0021    2.141  
A 3Σu+(1u) z+1000.49 482.15 Z 2.56  0.2259 21 0.0014    2.161  
A' 3Δu ,i 
A' 3Δu,i z+ 383 488.16 Z 2.51  0.2285 0.0014    2.148  
z 22 488.25 Z 2.52  0.2285 0.0015      
StateTeωeωexeωeyeBeαeγeDeβereTrans.ν00
b 1Σg+ y (699.7) 23 (3.4) 23         
a 1Δg x 24 702.35 Z 3.09  0.29262 0.00173  (2.01E-7)  1.8983  
X 3Σg- 0 25 725.65 Z 2.844  0.29547 26 0.001570 27 -1.82E-6 [1.90E-7]  1.8892 28  
↳Yee, Barrow, et al., 1972; Freedman and Jones, 1975
EPR and
↳Wayne, Davies, et al., 1974
mol. Beam rf sp.
↳Channappa, Pendlebury, et al., 1967

Notes

1Measurements of Mahajan, Lakshminarayana, et al., 1976; assignments of higher members of the two progressions appear uncertain.
2The two states E and F are believed to be members of two Rydberg series, one converging to X 2Π1/2 of S2+ (C,E,...), the other to X 2Π3/2 (F...). The apparent doublet structure of the bands is tentatively attributed to (ΩOc, w) coupling Donovan, Husain, et al., 1970.
3Only v=0 observed.
4The lower state(s) of the three systems could be either a or b; see Barrow and du Parcq, 1965, Barrow and Du Parcq, 1968. Bands originating from the j level have double heads, all others single heads. No absorption corresponding to these transitions has been reported, although strong absorption from a 1Δg (g←a, f←a) has been seen in the flash photolysis of S2Cl2 Donovan, Husain, et al., 1968, Donovan, Husain, et al., 1970 and COS Carleer and Colin, 1970. Tanaka and Ogawa, 1962 use c and c' instead of h and i, respectively.
5Called d →x by Tanaka and Ogawa, 1962. Observed in absorption in the flash photolysis of S2Cl2 Donovan, Husain, et al., 1970.
6v=0 only; system e-X of Tanaka and Ogawa, 1962.
7Spin splitting constants λ0 = -11.61, γ0 = +0.033.
8missing note
9Breaking-off in emission above v'= 10 Asundi, 1965, Narasimham and Gopal, 1965. In absorption Carleer and Colin, 1970 bands with v'=11 and 12 have been observed, the rotational lines being only very slightly broadened. Predissociation probably into 3Δu from 3P + 1D.
10First observed by Rosen and Desirant, 1935, Haranath, 1963. Vibrational numbering established by isotope investigations Narasimham and Brody, 1964, Narasimham and Bhagvat, 1965.
11The last observed levels in emission are J'=33 and 15 in 3Π2 and 3Π1, respectively; higher levels, and presumably all levels of the unobserved 3Π0 component, are predissociated.
12Fragments of two V shaded emission bands at v0 = 13451.9 and 13985.5 cm-1 have been observed by Meakin and Barrow, 1962 and assigned Barrow and du Parcq, 1965 to a 1Πg → 1Σu- transition later called e →c Barrow and Du Parcq, 1968. The first band (B' ~ 0.244, B"~ 0.229, predissociated except for low J) is undoubtedly the 0-0 band of the B' 3Πgl → A 3Σu+(0u-) transition, the second presumably the corresponding 1-0 band since the ΔG(1/2) value agrees fairly well with we ~ 500 as estimated from isotope shift studies Narasimham and Apparao, 1966. However, no emission from levels having v'> 0 was reported by other investigators.
13Origins of the 3Π2g → 3Σu+(1u) and 3Π1g → 3Σu+(0u-) transitions.
14Vibrational constants from Olsson, 1938, rotational constants from Ikenoue, 1960. Barrow and du Parcq, 1965 give B0 = 0.2235, αe = 0.0018, (i.e. Be = 0.2244) without mentioning whether this is based on a revised analysis. This state is heavily perturbed by a 3Πu state Barrow and du Parcq, 1965; as a result none of the constants are very meaningful.
15Spin splitting constant λ ~ -4.7 for v=0,2,4 (v=6,7 are also inverted) but +9.5 for v=1,3,5 Meyer and Crosley, 1973; see 14. Barrow and du Parcq, 1965 give γ=0.05 for v=0,1,4.
16Breaking-off in emission (at low pressures) above J=61 in v = 8, and J=36 in v=9 (F1 component) Ricks and Barrow, 1969, 2. J=58 in v = 8, and J=37 in v=9 (F2 component) Ricks and Barrow, 1969, 2. J=59 in v = 8, and J=35 in v=9 (F3 component) Ricks and Barrow, 1969, 2. These together with similar breaking-off points in 34S2 and 32S34S yield a predissociation limit at 35636.3 cm-1 above X 3Σg- (v=0,J=0) of 32S2. Bands with v'≥10 are absent in emission [except at high pressure Asundi, 1931, Asundi, 1934, Sugden and Demerdache, 1962] and broadened in absorption. Above v'=18 there is strongly increased diffuseness indicating a second predissociation Herzberg and Mundie, 1940. Pressure effects on the intensity distribution of the absorption bands Kondratjew and Olsson, 1936, Herman and Felenbok, 1963.
17Lifetime τ(v=0...3) = 17 ns Smith, 1969 [phase shift method Smith, 1969]; τ(v=3,4) = 19.5 ns Meyer and Crosley, 1973, 2 [Hanle effect Meyer and Crosley, 1973, 2]. The most recent measurements [single-photon time correlation McGee and Weston, 1977] give τ = 45.0 ns McGee and Weston, 1977.
18Secondary heads on the short-wavelength side of the bands are formed by the forbidden T(R31) branches [ Meakin and Barrow, 1962, see also Tatum and Watson, 1971]. Experimental Franck-Condon factors (v"=0...25) from resonance fluorescence series with v'=3,4 Meyer and Crosley, 1973, 3, see also Yee, Barrow, et al., 1972. Theoretical Franck-Condon factors Herman and Felenbok, 1963, Smith and Liszt, 1971 [see, however, 14] 32S2/34S2 isotope shifts Chaudhry, Upadhya, et al., 1970. Absorption in inert gas matrices at low temperature Brewer, Brabson, et al., 1965.
19The observed position of v'=0 relative to X 3Σg-(v"=0) is at 31659 cm-1; strong vibrational perturbation.
20Λ = -39.0 (and γ = +0.008) derived fron the observed F1(N) - F2(N) splittings Narasimham, Apparao, et al., 1976.
21B+(F2) - B-(F1) = +0.0021.
22z ~ 22000 cm-1, very rough estimate based on the fact that the upper state of B'→ A' is predissociated and, therefore, cannot lie below the dissociation limit 3P+ 3P. A similar value is obtained by extrapolation of the vibrational levels in A' and X to their common limit 3P + 3P.
23Assuming that b is the lower state of the three singlet systems originating from h, i, j.
24 Carleer and Colin, 1970 estimate x ~ 4700 cm-1.
25Refers to the F2 component.
26Spin splitting constants λv= +11.82+0.05(v+1/2) + 0.0024(v+1/2)2, γv= - 0.00659-0.000126(v+1/2), v≤27, from Barrow and Yee, 1974 who give also data for 34S2; see also Barrow and Ketteringham, 1963, Barrow and du Parcq, 1965, Wayne, Davies, et al., 1974. From the pure rotational Raman spectrum Freedman and Jones, 1975 obtain B0 = 0.29443.
27missing note
28Raman sp. 1
29From the predissociation limit in B 3Σu- assuming dissociation at this limit into 3P2 + 3P1 Ricks and Barrow, 1969, 2. The value given here (35240.2 cm-1) is relative to the lowest existing level in X 3Σg-(v=0), i.e. J=0, in accordance with the definition of D00 but at variance with the value given by Ricks and Barrow, 1969, 2 which refers to a hypothetical level (N=0) of the F2 component at 23.1 cm-1 above J=0. D00=4.38 eV by photoionization mass-spectrometry Berkowitz and Chupka, 1969, D00= 4.41 eV from thermal measurements Budininkas, Edwards, et al., 1968. See also Drowart and Goldfinger, 1966.
30By photoionization mass-spectrometry Berkowitz and Lifshitz, 1968, Berkowitz and Chupka, 1969.
31This number, given or implied by Barrow and du Parcq, 1965, Barrow, duParcq, et al., 1969 refers presumably to the F2 levels in both upper and lower state.
32Raman spectra in solid matrices Barletta, Claassen, et al., 1971, Hopkins and Brown, 1975 yield ΔG = 717 Barletta, Claassen, et al., 1971, Hopkins and Brown, 1975.

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.

Mahajan, Lakshminarayana, et al., 1976
Mahajan, C.G.; Lakshminarayana, G.; Narasimham, N.A., Rydberg transitions of S2, Indian J. Pure Appl. Phys., 1976, 14, 488. [all data]

Donovan, Husain, et al., 1970
Donovan, R.J.; Husain, D.; Stevenson, C.D., Vacuum ultra-violet spectra of transient molecules and radicals. Part 1. CS and S2, J. Chem. Soc. Faraday Trans., 1970, 66, 1. [all data]

Tanaka and Ogawa, 1962
Tanaka, Y.; Ogawa, M., Emission spectrum of S2 in the vacuum ultraviolet region, J. Chem. Phys., 1962, 36, 726. [all data]

Ricks and Barrow, 1969
Ricks, J.M.; Barrow, R.F., The D3Π state of S2, J. Phys. B:, 1969, 2, 906. [all data]

Barrow and Du Parcq, 1968
Barrow, R.F.; Du Parcq, R.P., 1Δu-1Δg transitions in gaseous S2, J. Phys. B:, 1968, 1, 283. [all data]

Wieland, Wehrli, et al., 1934
Wieland, K.; Wehrli, M.; Miescher, E., Ein neues absorptionsspektrum von zweiatomarem schwefeldampf im Schumanngebiet, Helv. Phys. Acta, 1934, 7, 843. [all data]

Carleer and Colin, 1970
Carleer, M.; Colin, R., The f1Δu-a1Δg band system of S2 in absorption, J. Phys. B:, 1970, 3, 1715. [all data]

Narasimham, 1964
Narasimham, N.A., The emission spectrum of S2 molecule, Curr. Sci., 1964, 33, 261. [all data]

Narasimham and Apparao, 1966
Narasimham, N.A.; Apparao, K.V.S.R., Isotope shifts in the near infra-red bands of diatomic sulphur, Nature (London), 1966, 210, 1034. [all data]

Meakin and Barrow, 1962
Meakin, J.E.; Barrow, R.F., The electronic spectrum of S2, Can. J. Phys., 1962, 40, 377. [all data]

Olsson, 1938
Olsson, Dissertation, Stockholm, 1938, 0. [all data]

Ikenoue, 1960
Ikenoue, K., Rotational structure of the band spectrum of S2 molecule. Part II., Sci. Light (Tokyo), 1960, 9, 79. [all data]

Barrow and du Parcq, 1965
Barrow, R.F.; du Parcq, R.P., Electronic spectrum and electronic states of S2 in Elemental Sulphur, Meyer, ed(s)., Interscience, New York, 1965, 251-263. [all data]

Yee, Barrow, et al., 1972
Yee, K.K.; Barrow, R.F.; Rogstad, A., Resonance fluorescence and Raman spectra of gaseous sulphur, J. Chem. Soc. Faraday Trans. 2, 1972, 68, 1808. [all data]

Freedman and Jones, 1975
Freedman, P.A.; Jones, W.J., Rotational Raman spectrum of sulphur dimer, J. Chem. Soc. Faraday Trans. 2, 1975, 71, 286. [all data]

Wayne, Davies, et al., 1974
Wayne, F.D.; Davies, P.B.; Thrush, B.A., The gas-phase E.P.R. spectrum of diatomic sulphur molecules, Mol. Phys., 1974, 28, 989. [all data]

Channappa, Pendlebury, et al., 1967
Channappa, K.H.; Pendlebury, J.M.; Smith, K.F., Atomic beam radiofrequency spectroscopy of S32 S32 molecules in La structure hyperfine magnetique des atomes et des molecules, Moser and Lefebvre, ed(s)., Paris, 1967, 73-81. [all data]

Donovan, Husain, et al., 1968
Donovan, R.J.; Husain, D.; Jackson, P.T., Transient species in the photolysis of sulphur monochloride, including S2(a 1? g )., Trans. Faraday Soc., 1968, 64, 1798, https://doi.org/10.1039/tf9686401798 . [all data]

Asundi, 1965
Asundi, R.K., Quantum characterization of electronic levels in molecules, J. Chem. Phys., 1965, 43, 24. [all data]

Narasimham and Gopal, 1965
Narasimham, N.A.; Gopal, K.S., On Rosen-Desirant ultra-violet bands of sulphur, Curr. Sci., 1965, 34, 454. [all data]

Rosen and Desirant, 1935
Rosen, B.; Desirant, M., Note au sujet de quelques nouveaux systemes de bandes observes dans les vapeurs de soufre et de selenium, Bull. Soc. R. Sci. Liege, 1935, 4, 233. [all data]

Haranath, 1963
Haranath, P.B.V., A new emission band spectrum of sulphur, Z. Phys., 1963, 173, 428. [all data]

Narasimham and Brody, 1964
Narasimham, N.A.; Brody, J.K., On the fine structure of the ultraviolet bands of S2, Proc. Indian Acad. Sci. Sect. A, 1964, 59, 345. [all data]

Narasimham and Bhagvat, 1965
Narasimham, N.A.; Bhagvat, K.M.N., Vibrational analysis of 2620 Å and 2760 Å bands of 32S34S, Proc. Indian Acad. Sci. Sect. A, 1965, 61, 75. [all data]

Meyer and Crosley, 1973
Meyer, K.A.; Crosley, D.R., Rotational satellite intensities and triplet splitting in the B3Σu- state of S2, Can. J. Phys., 1973, 51, 2119. [all data]

Ricks and Barrow, 1969, 2
Ricks, J.M.; Barrow, R.F., The dissociation energy of gaseous diatomic sulfur, Can. J. Phys., 1969, 47, 2423. [all data]

Asundi, 1931
Asundi, R.K., The emission bands of sulphur, Nature (London), 1931, 127, 93. [all data]

Asundi, 1934
Asundi, R.K., Additional bands in the band system of sulphur, Curr. Sci., 1934, 3, 154. [all data]

Sugden and Demerdache, 1962
Sugden, T.M.; Demerdache, A., Emission spectra of sulphur, Nature (London), 1962, 195, 596. [all data]

Herzberg and Mundie, 1940
Herzberg, G.; Mundie, L.G., On the predissociation of several diatomic molecules, J. Chem. Phys., 1940, 8, 263. [all data]

Kondratjew and Olsson, 1936
Kondratjew, V.; Olsson, E., Die induzierte pradissoziation im absorptionsspektrum des schwefels, Z. Phys., 1936, 99, 671. [all data]

Herman and Felenbok, 1963
Herman, L.; Felenbok, P., Effet des collisions sur la predissociation de S2, J. Quant. Spectrosc. Radiat. Transfer, 1963, 3, 247. [all data]

Smith, 1969
Smith, W.H., Absolute transition probabilities for some electronic states of CS, SO and S2, J. Quant. Spectrosc. Radiat. Transfer, 1969, 9, 1191. [all data]

Meyer and Crosley, 1973, 2
Meyer, K.A.; Crosley, D.R., Hanle effect lifetime measurements on selectively excited diatomic sulfur, J. Chem. Phys., 1973, 59, 1933. [all data]

McGee and Weston, 1977
McGee, T.H.; Weston, R.E., Jr., Lifetime of the B3Σu- state of S2, Chem. Phys. Lett., 1977, 47, 352. [all data]

Tatum and Watson, 1971
Tatum, J.B.; Watson, J.K.G., Rotational line strengths in 3Σ±-3Σ± transitions with intermediate coupling, Can. J. Phys., 1971, 49, 2693. [all data]

Meyer and Crosley, 1973, 3
Meyer, K.A.; Crosley, D.R., Franck-Condon factors from selectively excited resonance fluorescence in the B-X system of S2, J. Chem. Phys., 1973, 59, 3153. [all data]

Smith and Liszt, 1971
Smith, W.H.; Liszt, H.S., Franck-Condon factors and absolute oscillator strengths for NH, SiH, S2 and SO, J. Quant. Spectrosc. Radiat. Transfer, 1971, 11, 45. [all data]

Chaudhry, Upadhya, et al., 1970
Chaudhry, A.K.; Upadhya, K.N.; Nair, K.P.R., Isotope shift in the bands of B3Σu - X3Σg system of S2 molecule, Indian J. Pure Appl. Phys., 1970, 8, 52. [all data]

Brewer, Brabson, et al., 1965
Brewer, L.; Brabson, G.D.; Meyer, B., UV absorption spectrum of trapped S2, J. Chem. Phys., 1965, 42, 1385. [all data]

Narasimham, Apparao, et al., 1976
Narasimham, N.A.; Apparao, K.V.S.R.; Balasubramanian, T.K., Near-infrared bands of S2: 3Πgi-3Σu+ system, J. Mol. Spectrosc., 1976, 59, 244. [all data]

Barrow and Yee, 1974
Barrow, R.F.; Yee, K.K., The 3Σ- ground states of the group VI-VI molecules, O2, SO ..... Te2, Acta Phys. Acad. Sci. Hung., 1974, 35, 239. [all data]

Barrow and Ketteringham, 1963
Barrow, R.F.; Ketteringham, J.M., Triplet splitting in the ground state, X3Σg-, of S2, Can. J. Phys., 1963, 41, 419. [all data]

Berkowitz and Chupka, 1969
Berkowitz, J.; Chupka, W.A., Photoionization of high-temperature vapors. VI. S2, Se2, and Te2, J. Chem. Phys., 1969, 50, 4245. [all data]

Budininkas, Edwards, et al., 1968
Budininkas, P.; Edwards, R.K.; Wahlbeck, P.G., Dissociation energies of group VIa gaseous homonuclear diatomic molecules. I. Sulfur, J. Chem. Phys., 1968, 48, 2859. [all data]

Drowart and Goldfinger, 1966
Drowart, J.; Goldfinger, P., The dissociation energies of the group VIA diatomic molecules, Q. Rev. Chem. Soc., 1966, 20, 545. [all data]

Berkowitz and Lifshitz, 1968
Berkowitz, J.; Lifshitz, C., Photoionization of high temperature vapors. II. Sulfur molecular species, J. Chem. Phys., 1968, 48, 4346. [all data]

Barrow, duParcq, et al., 1969
Barrow, R.F.; duParcq, R.P.; Ricks, J.M., Rotational analysis of the C 3Σu--X 3g- system of 32S2, J. Phys. B:, 1969, 2, 413. [all data]

Barletta, Claassen, et al., 1971
Barletta, R.E.; Claassen, H.H.; McBeth, R.L., Raman spectrum of S2, J. Chem. Phys., 1971, 55, 5409. [all data]

Hopkins and Brown, 1975
Hopkins, A.G.; Brown, C.W., Additional evidence for the Raman band of S2, J. Chem. Phys., 1975, 62, 1598. [all data]

Notes

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