spackman_1991#
M. A. Spackman, “Time-dependent Hartree-Fock second-order molecular properties with a moderately sized basis set. I. The frequency dependence of the dipole polarizability”, J. Chem. Phys. 94, 1288 (1991)
Source record · Catalogue · Review register
DOI: 10.1063/1.460038
Source kind: theory
Recorded technique: Time-dependent coupled Hartree-Fock (RPA) calculations with CADPAC of the frequency-dependent mean polarizability and its anisotropy for 25 molecules, with the 6-31G(+sd+sp) basis and, for ten small molecules, Liu and Dykstra’s larger ‘electrical properties’ (ELP) basis; Cauchy moments from the RPA solution or, for butane, pentane and SF6, from a quartic fit of alpha(omega) in omega^2 (pp. 1288-1289). Compared with the DOSD moments of Meath and co-workers (Table I) and with Bogaard et al.’s and Alms et al.’s anisotropy dispersion (Table III).
Materials in structured entries: CH4, CO, CO2, H2, N2, N2O, SF6
Dataset quantities: cauchy_moment
Contents: 7 datasets; 0 formulas.
Curation notes#
Page numbers are the journal’s (1288-1294); pdf page 1 is the publisher’s cover, so p. = pdf page + 1286.
The TDHF moments are not used: they are theory that underestimates the dispersion systematically, ‘S(-2) and S(-4) ... are systematically underestimated by 20% and 40%’ (abstract, p. 1288); the rms deviation from the DOSD values is 27.6 % for S(-4) and 50.3 % for S(-6) with the small basis, and HF limit calculations ‘will typically underestimate the true values by more than 20%’ (pp. 1290-1291). For the curated species (6-31G(+sd+sp), ELP in parentheses; au): H2 alpha(0) 5.116 (5.091), S(-4) 16.84 (18.03), S(-6) 58.79 (68.55); CH4 15.771 (15.895), 50.07 (50.68), 199.11 (204.05); N2 10.773 (11.435), 24.73 (27.53), 69.48 (83.56); CO 11.357 (12.226), 36.78 (41.85), 213.23 (234.18); N2O 17.624, 50.80, 200.80; CO2 15.043 (15.731), 34.23 (37.49), 100.95 (118.85); SF6 26.041, 42.82, 110.39 (S(-4) 52 % and S(-6) 89 % below the DOSD, pp. 1290-1291). hohm_1993’s ‘Spackman [13]’ CH4 row mixes the two bases (ELP alpha(0), 6-31G S(-4), S(-6)).
Table I’s ‘Experiment’ columns (p. 1290, note b: ‘Experimental DOSD alpha(0), S(-4), and S(-6) from Meath et al. (Refs. 47-60)’) are reproductions and are extracted for the curated species (datasets meath_<gas>). The paper does not say which of Refs. 47-60 gives which molecule; the attributions are: H2, N2 and N2O equal zeiss_1977’s moments (5.428, 19.96, 82.94; 11.74, 30.11, 101.8; 19.70, 72.11, 410.7: checked); CH4 equals Thomas and Meath’s (Ref. 48; thomas_1977, curated since); CO and CO2 equal Jhanwar and Meath 1982’s (jhanwar_1982; CO 13.08, 48.27, 296.5 match it and not Kumar and Meath 1994’s 48.26, 292.9); SF6 equals Kumar, Fairley and Meath 1985’s electronic sums (kumar_1985b) (checked 2026-09-27). O2 is not treated (open shell, p. 1289).
Table II (p. 1291): other theory for H2, HF, H2O and N2 (CI, RPA, SOPPA, MCTDHF), with the DOSD S(-4), S(-6) repeated: not extracted. Table III (p. 1292): the dispersion delta[alpha] and delta[Delta alpha] between 632.8 and 488.0 nm and 100 rho_0 at 488.0 nm, experiment from Bogaard et al. (Ref. 63; not in the library) and, for N2, Alms et al. (alms_1975): N2 1.07, 0.10, 0.16; CO 0.52, 0.19, 0.21; CO2 4.12, 0.19, 0.29; N2O 6.12, 0.29, 0.58 (au); differences of polarizabilities between two wavelengths, which no quantity holds: not extracted. The paper argues that the measured anisotropy dispersion is overestimated for molecules with rho_0 < 1e-2, from a frequency-dependent vibrational Raman contribution (p. 1293).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
spackman_1991/meath_H2#
{
"id": "meath_H2",
"material": "H2",
"file": "H2/spackman_1991__meath_H2.csv",
"table": "tbl_6f890f395ef6",
"quantity": "cauchy_moment",
"unit": "au",
"abscissa": "order",
"abscissa_unit": "1",
"use": "reproduced",
"reproduced_from": [
"zeiss_1977"
]
}
Table I (p. 1290), ‘Experiment’: S(-2) = alpha(0), S(-4), S(-6) of Meath’s DOSD; equal to zeiss_1977/moments_H2.
spackman_1991/meath_CH4#
{
"id": "meath_CH4",
"material": "CH4",
"file": "CH4/spackman_1991__meath_CH4.csv",
"table": "tbl_6f890f395ef6",
"quantity": "cauchy_moment",
"unit": "au",
"abscissa": "order",
"abscissa_unit": "1",
"use": "reproduced",
"reproduced_from": [
"thomas_1977"
]
}
Table I, ‘Experiment’: Thomas and Meath’s moments (Ref. 48; the same values as hohm_1993/moments_thomas_1977_CH4): equal to thomas_1977’s S(-2) = 17.27, S(-4) = 62.41 (Table 2) and S(-6) = 298.3 (p. 121) (checked 2026-09-27).
spackman_1991/meath_N2#
{
"id": "meath_N2",
"material": "N2",
"file": "N2/spackman_1991__meath_N2.csv",
"table": "tbl_6f890f395ef6",
"quantity": "cauchy_moment",
"unit": "au",
"abscissa": "order",
"abscissa_unit": "1",
"use": "reproduced",
"reproduced_from": [
"zeiss_1977"
]
}
Table I, ‘Experiment’: equal to zeiss_1977/moments_N2.
spackman_1991/meath_CO#
{
"id": "meath_CO",
"material": "CO",
"file": "CO/spackman_1991__meath_CO.csv",
"table": "tbl_6f890f395ef6",
"quantity": "cauchy_moment",
"unit": "au",
"abscissa": "order",
"abscissa_unit": "1",
"use": "reproduced",
"reproduced_from": [
"jhanwar_1982"
]
}
Table I, ‘Experiment’: 13.08, 48.27, 296.5 au. Spackman does not name the paper among Refs. 47-60; the values equal jhanwar_1982’s CO sums (13.08, 48.27, 29.65(1)) and not Kumar and Meath 1994’s later 48.26 and 292.9 (kumar_1994), which Spackman (1991) predates (checked 2026-09-27).
spackman_1991/meath_N2O#
{
"id": "meath_N2O",
"material": "N2O",
"file": "N2O/spackman_1991__meath_N2O.csv",
"table": "tbl_6f890f395ef6",
"quantity": "cauchy_moment",
"unit": "au",
"abscissa": "order",
"abscissa_unit": "1",
"use": "reproduced",
"reproduced_from": [
"zeiss_1977"
]
}
Table I, ‘Experiment’: equal to zeiss_1977/moments_N2O.
spackman_1991/meath_CO2#
{
"id": "meath_CO2",
"material": "CO2",
"file": "CO2/spackman_1991__meath_CO2.csv",
"table": "tbl_6f890f395ef6",
"quantity": "cauchy_moment",
"unit": "au",
"abscissa": "order",
"abscissa_unit": "1",
"use": "reproduced",
"reproduced_from": [
"jhanwar_1982"
]
}
Table I, ‘Experiment’: 17.51, 50.99, 211.4 au, equal to jhanwar_1982’s electronic (UV) CO2 sums S(-2), S(-4), S(-6) = 17.51, 50.99, 21.14(1) (checked 2026-09-27); Spackman does not name the paper (Ref. 52 by the attribution through hohm_1994b’s row j).
spackman_1991/meath_SF6#
{
"id": "meath_SF6",
"material": "SF6",
"file": "SF6/spackman_1991__meath_SF6.csv",
"table": "tbl_6f890f395ef6",
"quantity": "cauchy_moment",
"unit": "au",
"abscissa": "order",
"abscissa_unit": "1",
"use": "reproduced",
"reproduced_from": [
"kumar_1985b"
]
}
Table I, ‘Experiment’: 30.04, 88.59, 982.1 au (the electronic DOSD; SF6’s large vibrational polarizability is not in it). Spackman does not name the paper; the values equal kumar_1985b’s electronic S(-2) = 3.004(1), S(-4) = 8.859(1) (Table II) and S(-6) = 982.1 (p. 73) (checked 2026-09-27).
Formulas#
No formulas are recorded.
Corrections#
No dataset errata are recorded in this source record.
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.