teal_1935#
G. K. Teal and G. E. MacWood, “The Raman spectra of the isotopic molecules H2, HD, and D2”, J. Chem. Phys. 3, 760 (1935)
Source record · Catalogue · Review register
DOI: 10.1063/1.1749589
Source kind: measurement
Recorded technique: Raman spectra of H2, HD and D2 gas at 3 atm in a fused-quartz cell, excited by Hg 2537 A (three low-pressure Hanovia arcs), photographed with a barostatted (739 mm) and thermostatted (32 C) Hilger E-1 quartz prism spectrograph, exposures of 100-200 hours, iron-arc reference; D2 samples of 99, 70 and 60 % deuterium (pp. 760-762).
Materials in structured entries: D2, H2
Dataset quantities: raman_shift, vibrational_term_value
Contents: 8 datasets; 2 formulas.
Curation notes#
Consulted for the D2 nuclear-spin statistics (TC-105). Page numbers are the journal’s (760-764); pdf page 1 is the publisher’s cover, so p. = pdf page + 758.
What the paper states about D2 (p. 764): ‘The measurement of the heights of the intensity maxima of the microphotometer curves of Plates I and II shows an alternation of intensities of the pure rotational lines of D2, the lines involving transitions from even states being more intense. This, in agreement with previous work on emission spectra, allows one to conclude that the deuterium nucleus obeys the Einstein-Bose statistics and has a spin different from zero. The semi-quantitative measurements agree very well with those expected according to Placzek’s theory if Murphy and Johnston’s value of the spin equal to 1 is used.’ No intensity ratio or spin weight is printed: the paper confirms, semi-quantitatively and in Raman scattering, the even-J-stronger alternation and murphy_1934’s spin 1, which give the 6 : 3 weights.
No refractive data. The Raman shifts, Delta G_1 and vibrational constants, left for later when this record was made, are now extracted (2026-09-26, below).
RAMAN LINES (Tables I and II, p. 763; tools/extract/teal_1935.py). ‘a comparison of the calculated and observed values of the frequencies in wave numbers in vacuum’ (p. 762): vacuum wavenumbers. Gas at 3 atm in the fused-quartz cell (the temperature is not stated; the spectrograph was thermostatted at 32 C). Material: H2 and D2 as the gases were (the paper says nothing of ortho:para; room-temperature H2 is normal); the D2 samples of Plates I, II and III were 99, 70 and 60 % deuterium (the rest mainly HD), which does not move the D2 lines. The rows are the printed J pairs, initial-final: in Table I ‘3-1’ is an anti-Stokes line and ‘1-3’ the Stokes line of the same levels, recorded separately (S(1) either way); in Table II ‘1-1’ is Q(1) and ‘0-2’ S(0) of the 0-1 band. The value taken is the AVERAGE column. Uncertainty (p. 762): ‘The error in measurement of the lines varies from 0.5 to 1.0 cm^-1 except for several very weak lines. It is estimated that the average values of the three plates are good to approximately 0.3 cm^-1’ (recorded as the absolute uncertainty, level not stated; many H2 lines were measured on Plate III alone, so they are nearer the single-plate 0.5-1.0 cm^-1). HD’s lines (Table I: 8 rotational lines 267.1-949.3 cm^-1; Table II: Q(0)-Q(4), 3630.8-3592.5 cm^-1, the Q(0) line ‘observed’ although theory forbids it, p. 764) are not taken: HD is not a curated material.
AVERAGES. Most AVERAGE cells are the mean of the plate columns; a few are not and the paper does not say how they were formed (weighted by plate?): D2 Table I 4-2 (plates 416.1 and 414.2, printed 415.0) and Table II 2-2 (2986.4, 2986.0, 2987.2: 2986.9), 3-3 (2980.1 for a mean of 2980.2) and 5-5 (2962.3 for 2962.6); in each of these the printed DIFFERENCE columns agree with the printed average, so they are kept. D2 Table I 3-1 is the exception: printed 297.3, while the plates (297.5, 297.5, 296.4) average 297.13 and the DIFFERENCE column prints -0.6 against CALC. 297.7, i.e. 297.1: an erratum (below). The DIFFERENCE columns otherwise reproduce AVERAGE - CALC. to +-0.1 (rounding).
CALCULATED VALUES. Table I’s CALC. column uses ‘the constants of Jeppesen as recalculated by Urey and Teal’ (p. 762; Rev. Mod. Phys. 3, 243 (1935) as printed): in ‘printed’ only. Table II gives two calculations: ‘U. & T.’ (the older constants, which leave the Q branch 2-4 cm^-1 too high: ‘it was concluded that the vibrational constants were incorrect’, p. 763) and ‘T. & M.’ (this paper’s constants of Table III), the table2_calc_* datasets (check), including the unobserved 0-0 lines, H2 4160.4 and D2 2993.2 (= Delta G_1 from the Table III constants). The energy expression (p. 762): E/hc = omega_e (v + 1/2) - x omega_e (v + 1/2)^2 + y omega_e (v + 1/2)^3 - z omega_e (v + 1/2)^4 + [B_e - alpha_e (v + 1/2) + gamma_e (v + 1/2)^2 - delta_e (v + 1/2)^3] J(J+1) + [D_e + beta_e (v + 1/2)] J^2(J+1)^2 + F_e J^3(J+1)^3. The rotational constants used are not printed (Urey and Teal’s).
DELTA G_1 (p. 763): ‘Our experimental values for Delta G_i are: Delta G_1(H2) = 4160.2 +- 0.2 cm^-1, Delta G_1(HD) = 3631.4 +- 0.2 cm^-1, Delta G_1(D2) = 2993.5 +- 0.2 cm^-1’ (level not stated): G(1) - G(0), the rotationless band origin, recorded as vibrational_term_value of v = 1 from v = 0 (the quantity whose meaning it is; it is not an observed line, the 0-0 lines of H2 and D2 being unobserved). The constants of Table III come from ‘Least-square solutions of the Delta G values for the first seven states’ of H2 (Jeppesen, Rasetti as recalculated by Birge and Jeppesen, and this study) and HD (Jeppesen, Mie, and this study), weighted 1 (emission), 3 (Rasetti) and 5 (this Raman data) (p. 763).
TABLE III (p. 764): omega_e, x omega_e, y omega_e, z omega_e (cm^-1) of H2, HD and D2, and the ratio rho’’ (H2-HD) observed against theory: omega_e 0.86648 / 0.86616, x omega_e 0.7577 / 0.7502, y omega_e 0.748 / 0.650, z omega_e 0.680 / 0.563 (notes only). ‘The molecular constants of D2 given in the table are the average values calculated from those of H2 and HD, assuming the theoretical relationships between the reduced masses ... to hold’ (p. 764): derived, not fitted to D2 lines. No quantity holds a vibrational constant such as omega_e: they are recorded as the vibrational-term formulas below (H2, and D2 as a check). HD’s: 3817.09, 94.958, 1.4569, 0.07665 (notes).
PRESSURE (p. 763): Rasetti’s H2 Q branch at about 12 atm disagrees with these 3 atm values; ‘The cause of the differences is not yet understood’; footnote: the N2 vibration line on Plate III was lower than Rasetti’s (12 atm) by about the same amount. The apparent frequency of the exciting Hg line from the Stokes and anti-Stokes pairs: 39 411.9, 39 412.43 and 39 412.35 cm^-1 on Plates I, II and III (p. 762).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
teal_1935/table1_H2#
{
"id": "table1_H2",
"material": "H2",
"file": "H2/teal_1935__table1_H2.csv",
"table": "tbl_cd69d07ceea3",
"quantity": "raman_shift",
"unit": "cm-1",
"abscissa": "label",
"use": "primary",
"parameters": {
"transition": "pure rotational, v = 0, J initial-final as the row (S branch)"
},
"uncertainty": {
"absolute": 0.3,
"level": "not stated"
}
}
Table I (p. 763): the pure rotational lines of H2 (v 0-0), the AVERAGE column, vacuum wavenumbers; rows the printed J pair initial-final (3-1 and 2-0 anti-Stokes; 0-2, 1-3, 2-4, 3-5 Stokes: S(0)-S(3)). All from Plate III except 1-3 (Plates II and III). 3 atm.
teal_1935/table1_D2#
{
"id": "table1_D2",
"material": "D2",
"file": "D2/teal_1935__table1_D2.csv",
"table": "tbl_cd69d07ceea3",
"quantity": "raman_shift",
"unit": "cm-1",
"abscissa": "label",
"use": "primary",
"parameters": {
"transition": "pure rotational, v = 0, J initial-final as the row (S branch)"
},
"uncertainty": {
"absolute": 0.3,
"level": "not stated"
}
}
Table I (p. 763): the pure rotational lines of D2 (v 0-0), the AVERAGE column, vacuum wavenumbers; rows the printed J pair initial-final (6-4 ... 2-0 anti-Stokes, 0-2 ... 5-7 Stokes: S(0)-S(5)). Row 3-1 corrected by an erratum (297.3 printed, 297.1). The paper notes ‘a trend in the values for D2 indicates that the rotational levels for this molecule may be closer together than predicted by theory’ (p. 762): the observed high-J lines lie 1.2-1.5 cm^-1 below the calculation. 3 atm.
teal_1935/table2_H2#
{
"id": "table2_H2",
"material": "H2",
"file": "H2/teal_1935__table2_H2.csv",
"table": "tbl_4c1e371a6dd6",
"quantity": "raman_shift",
"unit": "cm-1",
"abscissa": "label",
"use": "primary",
"parameters": {
"transition": "v = 0 -> 1, J initial-final as the row (Q branch)"
},
"uncertainty": {
"absolute": 0.3,
"level": "not stated"
}
}
Table II (p. 763): the Q(1)-Q(3) lines of the H2 0-1 band (rows 1-1, 2-2, 3-3), the AVERAGE column (Plate III only), vacuum wavenumbers. Q(1) = 4154.1 cm^-1. At 3 atm; the paper records a disagreement with Rasetti’s 12 atm values it cannot explain (p. 763).
teal_1935/table2_D2#
{
"id": "table2_D2",
"material": "D2",
"file": "D2/teal_1935__table2_D2.csv",
"table": "tbl_4c1e371a6dd6",
"quantity": "raman_shift",
"unit": "cm-1",
"abscissa": "label",
"use": "primary",
"parameters": {
"transition": "v = 0 -> 1, J initial-final as the row (Q and S branches)"
},
"uncertainty": {
"absolute": 0.3,
"level": "not stated"
}
}
Table II (p. 763): the D2 0-1 band, Q(1)-Q(6) (rows 1-1 ... 6-6) and S(0)-S(2) (rows 0-2, 1-3, 2-4), the AVERAGE column, vacuum wavenumbers. Q(2) = 2986.9 cm^-1. Some averages are not the plain mean of the plates (see the record’s notes).
teal_1935/table2_calc_H2#
{
"id": "table2_calc_H2",
"material": "H2",
"file": "H2/teal_1935__table2_calc_H2.csv",
"table": "tbl_4c1e371a6dd6",
"quantity": "raman_shift",
"unit": "cm-1",
"abscissa": "label",
"use": "check",
"parameters": {
"transition": "v = 0 -> 1, J initial-final as the row (Q branch)"
}
}
Table II (p. 763), ‘CALCULATED, T. & M.’: Q(0)-Q(3) of H2 from this paper’s vibrational constants (Table III) and Urey and Teal’s rotational constants; row 0-0 (4160.4) is the unobserved Q(0), i.e. Delta G_1 from the constants.
teal_1935/table2_calc_D2#
{
"id": "table2_calc_D2",
"material": "D2",
"file": "D2/teal_1935__table2_calc_D2.csv",
"table": "tbl_4c1e371a6dd6",
"quantity": "raman_shift",
"unit": "cm-1",
"abscissa": "label",
"use": "check",
"parameters": {
"transition": "v = 0 -> 1, J initial-final as the row (Q and S branches)"
}
}
Table II (p. 763), ‘CALCULATED, T. & M.’: the D2 0-1 band from this paper’s constants (the D2 ones derived from H2 and HD by isotope relations); row 0-0 (2993.2) is the unobserved Q(0) = Delta G_1 from the constants (p. 764).
teal_1935/text_deltaG1_H2#
{
"id": "text_deltaG1_H2",
"material": "H2",
"table": "text",
"quantity": "vibrational_term_value",
"unit": "cm-1",
"abscissa": "label",
"use": "primary",
"parameters": {
"reference": "v0"
},
"uncertainty": {
"column": true,
"level": "not stated"
}
}
1 inline points in the source record.
p. 763: ‘Delta G_1(H2) = 4160.2 +- 0.2 cm^-1’, ‘Our experimental values’: G(1) - G(0) (row v = 1, from v = 0), the rotationless band origin, from the Q-branch lines of this study. Level of the +-0.2 not stated. The Table III constants give 4160.4 (Table II, 0-0).
teal_1935/text_deltaG1_D2#
{
"id": "text_deltaG1_D2",
"material": "D2",
"table": "text",
"quantity": "vibrational_term_value",
"unit": "cm-1",
"abscissa": "label",
"use": "primary",
"parameters": {
"reference": "v0"
},
"uncertainty": {
"column": true,
"level": "not stated"
}
}
1 inline points in the source record.
p. 763: ‘Delta G_1(D2) = 2993.5 +- 0.2 cm^-1’, G(1) - G(0) (row v = 1, from v = 0), from the D2 Q-branch lines of this study. Level not stated. The Table III constants (derived from H2 and HD) give 2993.2, ‘only 0.1 cm^-1 more than the estimated accuracy’ away (p. 764).
Formulas#
teal_1935/vibrational_terms_H2#
{
"id": "vibrational_terms_H2",
"material": "H2",
"equation": "p. 762 (the energy expression) and Table III, p. 764",
"printed": "E/hc = omega_e (v + 1/2) - x omega_e (v + 1/2)^2 + y omega_e (v + 1/2)^3 - z omega_e (v + 1/2)^4 (+ the rotational terms, whose constants are not printed)",
"variable": "v: the vibrational quantum number; E/hc in cm^-1 from the potential minimum",
"range": "the first seven levels (v = 0-6), the Delta G values fitted",
"coefficients": {
"omega_e": "4405.30",
"x_omega_e": "125.325",
"y_omega_e": "1.9473",
"z_omega_e": "0.11265"
},
"coefficient_units": {
"omega_e": "cm^-1",
"x_omega_e": "cm^-1",
"y_omega_e": "cm^-1",
"z_omega_e": "cm^-1"
},
"check": "Delta G_1 = omega_e - 2 x omega_e + 3.25 y omega_e - 5 z omega_e = 4160.415 cm^-1, which is Table II's T. & M. Q(0) 4160.4, against the measured 4160.2 +- 0.2 (checked 2026-09-26)."
}
Table III (p. 764), H2 column: a least-squares fit of the Delta G values of v = 0-6 (emission data of Jeppesen weight 1, Rasetti’s Raman 3, this study 5; p. 763). Note the signs: + y omega_e, - z omega_e as printed.
teal_1935/vibrational_terms_D2#
{
"id": "vibrational_terms_D2",
"material": "D2",
"equation": "p. 762 (the energy expression) and Table III, p. 764",
"printed": "E/hc = omega_e (v + 1/2) - x omega_e (v + 1/2)^2 + y omega_e (v + 1/2)^3 - z omega_e (v + 1/2)^4",
"variable": "v: the vibrational quantum number; E/hc in cm^-1 from the potential minimum",
"range": "not stated (derived, not fitted to D2 levels)",
"coefficients": {
"omega_e": "3117.05",
"x_omega_e": "63.034",
"y_omega_e": "0.74526",
"z_omega_e": "0.031573"
},
"coefficient_units": {
"omega_e": "cm^-1",
"x_omega_e": "cm^-1",
"y_omega_e": "cm^-1",
"z_omega_e": "cm^-1"
},
"check": "Delta G_1 = 3117.05 - 126.068 + 2.4221 - 0.1579 = 2993.246 cm^-1, the printed 2993.2 (p. 764 and Table II's 0-0), against the measured 2993.5 +- 0.2 (checked 2026-09-26)."
}
Table III (p. 764), D2 column: ‘the average values calculated from those of H2 and HD, assuming the theoretical relationships between the reduced masses of H2 and D2 and of HD and D2 to hold’ (p. 764): an isotope-relation derivation, a check only, not a fit to D2 data.
Corrections#
[
{
"dataset": "table1_D2",
"row": "3-1",
"column": "value",
"printed": "297.3",
"corrected": "297.1",
"reason": "The AVERAGE of the D2 3-1 line is printed 297.3, but the three plate values beside it (297.5, 297.5, 296.4) average 297.13, and the table's own DIFFERENCE column prints -0.6 against CALC. 297.7, i.e. an average of 297.1. Every other row's DIFFERENCE agrees with its printed AVERAGE to rounding.",
"evidence": "Table I (p. 763), table image checked (tbl_cd69d07ceea3.jpg): the printed cells are 297.5, 297.5, 296.4, 297.3, 297.7, -0.6. An internal inconsistency; the paper has no erratum."
}
]
Formula corrections, where recorded, appear with their formulas above. Curation notes may also discuss corrections or unresolved interpretation. Consult the review register for the checks and decisions.