van_duijnen_1998#
P. Th. van Duijnen and M. Swart, “Molecular and Atomic Polarizabilities: Thole’s Model Revisited”, J. Phys. Chem. A 102, 2399-2407 (1998)
Source record · Catalogue · Review register
DOI: 10.1021/jp980221f
Source kind: compilation
Recorded technique: Thole’s modified dipole-interaction model: molecular polarizabilities built from isotropic atomic polarizabilities coupled by screened dipole-field tensors (linear and exponential charge distributions, Eqs. 1-9), the atomic polarizabilities and the screening length fitted to ‘experimental’ mean molecular polarizabilities of Thole’s original learning set (16 molecules, control set 6) and of an extended set of 52 molecules (control 18), and to CPHF, second-order and Unsoeld ab initio polarizabilities in six basis sets (HONDO 8.1).
Materials in structured entries: CH4, CO, CO2, H2, N2, N2O, O2, SF6
Dataset quantities: polarizability
Contents: 9 datasets; 0 formulas.
Curation notes#
Record UNVERIFIED in the library: title, authors, journal, volume and issue from the first page (pdf p. 1: ‘J. Phys. Chem. A, Volume 102, Number 14, April 2, 1998’; received November 14, 1997); the page range is not printed in the library text and is not given here. The DOI is inferred from the pdf’s file name, jp980221f.pdf (the ACS manuscript number), not printed (TC-154).
The curated species appear only in the ‘exp’ columns, the experimental mean static polarizabilities (au) the model is fitted to. NO SOURCES ARE GIVEN for them, and their wavelength is uncertain: ‘Experimental data are usually obtained from the Lorentz-Lorentz equation ... with the refractive index n (usually at 5893 A, sodium D line) ... an extrapolation of the refractive index to zero frequency (or infinite wavelength) should be made ... As a result of this extrapolation, the polarizabilities decrease within 2-4 %, which gives an estimate of the uncertainty in the experimental data. The values obtained at 5893 A are used throughout this article’ (p. 4). They are stored at 5893 A (standard air, the sodium D line as usually quoted). Table 1’s are Thole’s original learning and control sets (‘We started by repeating Thole’s work, i.e., the same learning set and the same set of test cases’, p. 5).
ALL EXCLUDED: values of unstated origin and wavelength, printed to four figures, no uncertainty; against the curated fits at 589.3 nm (air) they scatter by -4.0 % (H2), -0.33 % (N2), -0.04 % (O2), +0.19 % (CH4, Table 1) or +1.2 % (CH4, Table 11), -0.38 % (CO2), -0.57 % (SF6), +0.58 % (N2O) (fit/<gas> models, checked 2026-09-25). H2’s 5.33 au is below even the static value (fit/H2: 5.43 au). Kept for the record. CO (added 2026-09-25, before the CO model): 13.16 au in Tables 1 and 11, 0.8 % above zhao_2026’s static 13.059 au and about 1.5 % below that value plus Kumar and Meath’s electronic dispersion to 589.3 nm (about 13.36 au, computed 2026-09-25 from zhao_2026’s quoted S(-4), S(-6), S(-8)).
Methane is 17.68 au in Tables 1, 3 and 9 but 17.86 in Table 11 (image checked). Not a misprint in either table: Table 1’s own deviations (linear model 17.46, ‘1.26 %’) reproduce 17.68, and Table 11’s alkane-group deviations (2.64 and 1.57 %) reproduce 17.86 (2.53 and 1.46 % with 17.68): the extended fit used 17.86 (checked 2026-09-25). Both are stored.
Not extracted: the fitted atomic polarizabilities and screening lengths (Tables 2, 4, 6, 7), the model and CPHF/SOP/Unsoeld columns (Tables 1, 3, 9, 11), the tensor components of Table 12, Tables 5 and 8 (percentages).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
van_duijnen_1998/table1_CO#
{
"id": "table1_CO",
"material": "CO",
"file": "CO/van_duijnen_1998__table1_CO.csv",
"table": "tbl_3b0fee402144",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"B. T. Thole, Chem. Phys. 59, 341 (1981) (the learning set's experimental values; their own sources are not given)"
]
}
Table 1 ‘exp’ (learning set): 13.16 au; Table 11 prints the same value (not written twice). Excluded: origin and wavelength unstated (‘usually at 5893 A’, p. 4); between the static and the 589 nm electronic values implied by zhao_2026 (source notes).
van_duijnen_1998/table1_H2#
{
"id": "table1_H2",
"material": "H2",
"file": "H2/van_duijnen_1998__table1_H2.csv",
"table": "tbl_3b0fee402144",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"B. T. Thole, Chem. Phys. 59, 341 (1981) (the learning set's experimental values; their own sources are not given)"
]
}
Table 1 ‘exp’ (learning set): 5.33 au. Excluded: origin and wavelength unstated (‘usually at 5893 A’, p. 4); 4.0 % below fit/H2 at 589 nm and below the static value.
van_duijnen_1998/table1_N2#
{
"id": "table1_N2",
"material": "N2",
"file": "N2/van_duijnen_1998__table1_N2.csv",
"table": "tbl_3b0fee402144",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"B. T. Thole, Chem. Phys. 59, 341 (1981) (the learning set's experimental values; their own sources are not given)"
]
}
Table 1 ‘exp’ (learning set): 11.88 au (also Table 11). Excluded: origin and wavelength unstated (‘usually at 5893 A’, p. 4); -0.33 % against fit/N2 at 589 nm.
van_duijnen_1998/table1_O2#
{
"id": "table1_O2",
"material": "O2",
"file": "O2/van_duijnen_1998__table1_O2.csv",
"table": "tbl_3b0fee402144",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"B. T. Thole, Chem. Phys. 59, 341 (1981) (the learning set's experimental values; their own sources are not given)"
]
}
Table 1 ‘exp’ (learning set): 10.80 au (also Table 11). Excluded: origin and wavelength unstated (‘usually at 5893 A’, p. 4); -0.04 % against fit/O2 at 589 nm.
van_duijnen_1998/table1_CH4#
{
"id": "table1_CH4",
"material": "CH4",
"file": "CH4/van_duijnen_1998__table1_CH4.csv",
"table": "tbl_3b0fee402144",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"B. T. Thole, Chem. Phys. 59, 341 (1981) (the control set's experimental values; their own sources are not given)"
]
}
Table 1 ‘exp’ (control set): 17.68 au (also Tables 3 and 9; Table 11 prints 17.86, see table11_CH4). Excluded: origin and wavelength unstated (‘usually at 5893 A’, p. 4); +0.19 % against fit/CH4 at 589 nm.
van_duijnen_1998/table11_CH4#
{
"id": "table11_CH4",
"material": "CH4",
"file": "CH4/van_duijnen_1998__table11_CH4.csv",
"table": "tbl_737b997b82b0",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"sources not given (van Duijnen and Swart's extended learning set)"
]
}
Table 11 ‘exp’: 17.86 au, used in the extended fit (the group deviations reproduce it) but differing from Table 1’s 17.68 for the same molecule. Excluded: +1.2 % against fit/CH4 at 589 nm; origin unstated.
van_duijnen_1998/table11_CO2#
{
"id": "table11_CO2",
"material": "CO2",
"file": "CO2/van_duijnen_1998__table11_CO2.csv",
"table": "tbl_f45b9a639abe",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"sources not given (van Duijnen and Swart's extended learning set)"
]
}
Table 11 (continued) ‘exp’: 17.75 au. Excluded: origin and wavelength unstated; -0.38 % against fit/CO2 at 589 nm (an optical value: the static total is 19.65 au).
van_duijnen_1998/table11_SF6#
{
"id": "table11_SF6",
"material": "SF6",
"file": "SF6/van_duijnen_1998__table11_SF6.csv",
"table": "tbl_f45b9a639abe",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"sources not given (van Duijnen and Swart's extended learning set)"
]
}
Table 11 (continued) ‘exp’: 30.17 au. Excluded: origin and wavelength unstated; -0.57 % against fit/SF6 at 589 nm (an optical value: the static total is 44.0 au).
van_duijnen_1998/table11_N2O#
{
"id": "table11_N2O",
"material": "N2O",
"file": "N2O/van_duijnen_1998__table11_N2O.csv",
"table": "tbl_f45b9a639abe",
"quantity": "polarizability",
"unit": "au",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "excluded",
"reproduced_from": [
"sources not given (van Duijnen and Swart's extended control set, italic in Table 11)"
]
}
Table 11 (continued) ‘exp’, control set (italic): 20.24 au. Excluded: origin and wavelength unstated; +0.58 % against fit/N2O at 589 nm, between the optical and the static values (Töpfer et al. 2023, topfer_2023, quote the same 2.998 A^3 = 20.23 au from Olney et al. 1997).
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.