reinsch_1985#

E.-A. Reinsch, J. Chem. Phys. 83, 5784 (1985)

Source record · Catalogue · Review register

Source kind: theory

Recorded technique: Time-dependent perturbation theory for multiconfiguration SCF (MC-SCF) wave functions (a multiconfigurational time-dependent Hartree-Fock linear response, solved through the MC-SCF Hessian), nonrelativistic, clamped nuclei. He and H2: five-configuration MC-SCF in Huzinaga-based Gaussian basis sets; Ne, HF, H2O, NH3, CH4: 45-configuration MC-SCF (all double excitations from the four valence orbitals into the first four virtuals of the same symmetry) in Werner and Meyer’s basis B with d sets; for Ne also an extended basis (one more s, p and d set, zeta = 0.055). CH4 at r_CH = 2.061 bohr. H2 at R = 1.2-1.6 bohr, with vibrational averaging by P. Botschwina (pp. 5788-5790).

Materials in structured entries: CH4, H2, He, Ne

Dataset quantities: polarizability

Contents: 21 datasets; 0 formulas.

Curation notes#

omega is in hartree (Table I note a: ‘all omega values in this paper are given in hartree’, p. 5788), polarizabilities in atomic units (bohr^3). Electronic polarizabilities only (no vibrational contribution, no magnetic susceptibility). Journal pages 5784-5791 = pdf pages 2-9 (pdf page 1 is a cover sheet).

Accuracy (the author’s): for He ‘agreement within 1% up to omega = 0.65’ with Chung’s and Starkschall and Gordon’s values; the correlation contribution at omega = 0 is 4.6 % (p. 5788). For the ten-electron systems the 45-configuration MC-SCF recovers 65-90 % of the correlation contribution at omega = 0 (Table VI); for Ne ‘the error in the polarizability increases from 4% (omega = 0) to 7.5% (omega = 0.35)’, reduced with the extended basis (p. 5790); ‘the absolute accuracy for the latter case is in the range of 4% to 9.5%’ (abstract). All of this work’s values are therefore stored as checks, not for fitting (the He MC-SCF column could be promoted).

Reproduced comparison values: He Chung (Ref. 6 as cited by Ref. 20), Starkschall and Gordon (Ref. 20, moment theory from experiment), ‘Expt’ as fitted by Pade approximants (Ref. 21, Langhoff and Karplus 1969 = langhoff_1969); Ne ‘Expt’ (Table III note a: ‘as cited by Ref. 20’, while the text p. 5790 says ‘the experimental values for Ne as given by Langhoff and Karplus (Ref. 21)’); Ne static SCF, PNO-CI and CEPA of Werner and Meyer (Ref. 5; Table VI, ‘without vibrational correction’); CH4 ‘Exp’ computed by the author from Landolt-Bornstein’s two-term fits C_1/(nu_1^2 - nu^2) + C_2/(nu_2^2 - nu^2) (Table V note c), so an evaluation of a dispersion formula, not measurements; CH4 PNO-CI/CEPA 16.39/16.53 of Werner and Meyer (Table V note f).

H2 (Table II): the upper block gives alpha_parallel and alpha_perp at fixed internuclear distances R = 1.2-1.6 bohr (not extracted: tensor components at fixed R; anisotropies are for later). The lower block (the mean at R = 1.4 bohr, this work and Victor, Browne and Dalgarno; the vibrationally averaged alpha_parallel, alpha_perp and mean for v = 0, the mean for v = 1 and the 0-1 transition; experiment) is MISSING from the library’s cells file; its values are entered inline, read from the table image and checked on the pdf page (p. 5789): the printed means equal (alpha_parallel + 2 alpha_perp)/3 of the printed components to the last digit (R = 1.4: 5.203, 5.392, 6.061, 7.740; v = 0: 5.438, 5.646, 6.399, 8.370), which confirms the reading. Table II notes: b, c Kolos and Wolniewicz (Ref. 22) static alpha_parallel 6.3805 and alpha_perp 4.5777 at R = 1.4; f their vibrationally averaged mean 5.414 (v = 0, static). Anisotropy kappa 0.125 against the experimental 0.128 (p. 5789).

Not extracted: HF, H2O, NH3 (not curated species); the He excitation energies and C_6 (p. 5789), the Ne C_6 6.158 (p. 5790).

Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.

Datasets#

reinsch_1985/mcscf_He#

{
  "id": "mcscf_He",
  "material": "He",
  "file": "He/reinsch_1985__mcscf_He.csv",
  "table": "tbl_26de7c6c1f20",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "check"
}

Table I ‘This work MC-SCF’: alpha(omega), omega = 0-0.75 hartree, 11 points; within 1 % of Chung up to omega = 0.65 (p. 5788).

reinsch_1985/scf_He#

{
  "id": "scf_He",
  "material": "He",
  "file": "He/reinsch_1985__scf_He.csv",
  "table": "tbl_26de7c6c1f20",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "excluded"
}

Table I ‘This work SCF’ (coupled Hartree-Fock level): 4.6 % low at omega = 0 (no correlation). Kept for the record; excluded.

reinsch_1985/chung_He#

{
  "id": "chung_He",
  "material": "He",
  "file": "He/reinsch_1985__chung_He.csv",
  "table": "tbl_26de7c6c1f20",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "K. T. Chung, Phys. Rev. 166, 1 (1968), as cited by G. Starkschall and R. G. Gordon, J. Chem. Phys. 54, 663 (1971)"
  ]
}

Table I ‘Chung’ (note b: Ref. 6 cited in Ref. 20): variational theory, ‘the best theoretical values available’ (p. 5788), 11 points.

reinsch_1985/starkschall_gordon_He#

{
  "id": "starkschall_gordon_He",
  "material": "He",
  "file": "He/reinsch_1985__starkschall_gordon_He.csv",
  "table": "tbl_26de7c6c1f20",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "G. Starkschall and R. G. Gordon, J. Chem. Phys. 54, 663 (1971)"
  ]
}

Table I ‘St&G’ (note c): ‘obtained from experimental values by the moment theory’ (p. 5788), 11 points; the 0.75 hartree value is printed with three digits (8.38).

reinsch_1985/expt_He#

{
  "id": "expt_He",
  "material": "He",
  "file": "He/reinsch_1985__expt_He.csv",
  "table": "tbl_26de7c6c1f20",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "langhoff_1969"
  ]
}

Table I ‘Expt’ (note d: ‘As fitted by Pade approximants (Ref. 21)’), 8 points: Langhoff and Karplus’s Pade representation of experimental refractivity, evaluated by the author.

reinsch_1985/mcscf_standard_Ne#

{
  "id": "mcscf_standard_Ne",
  "material": "Ne",
  "file": "Ne/reinsch_1985__mcscf_standard_Ne.csv",
  "table": "tbl_e741f654ef3f",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "check"
}

Table III ‘This work Sbs.’ (standard basis), omega = 0-0.40 hartree, 9 points; 4 % low at omega = 0, 7.5 % at 0.35 (p. 5790).

reinsch_1985/mcscf_extended_Ne#

{
  "id": "mcscf_extended_Ne",
  "material": "Ne",
  "file": "Ne/reinsch_1985__mcscf_extended_Ne.csv",
  "table": "tbl_e741f654ef3f",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "check"
}

Table III ‘This work Ebs.’ (extended basis, one more s, p, d set with zeta = 0.055), 9 points.

reinsch_1985/expt_Ne#

{
  "id": "expt_Ne",
  "material": "Ne",
  "file": "Ne/reinsch_1985__expt_Ne.csv",
  "table": "tbl_e741f654ef3f",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "G. Starkschall and R. G. Gordon, J. Chem. Phys. 54, 663 (1971)",
    "langhoff_1969"
  ]
}

Table III ‘Expt’ (note a: ‘as cited by Ref. 20’; the text, p. 5790, attributes the experimental Ne values to Langhoff and Karplus, Ref. 21), omega = 0.20-0.35 hartree, 4 points.

reinsch_1985/mcscf_static_Ne#

{
  "id": "mcscf_static_Ne",
  "material": "Ne",
  "file": "Ne/reinsch_1985__mcscf_static_Ne.csv",
  "table": "tbl_c3d0b718917c",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "excluded"
}

Table VI ‘MC-SCF’ (this work) 2.567 at omega = 0: the Table III standard-basis value 2.5671 rounded (duplicate; excluded).

reinsch_1985/werner_meyer_scf_Ne#

{
  "id": "werner_meyer_scf_Ne",
  "material": "Ne",
  "file": "Ne/reinsch_1985__werner_meyer_scf_Ne.csv",
  "table": "tbl_c3d0b718917c",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "H.-J. Werner and W. Meyer, Mol. Phys. 31, 855 (1976)"
  ]
}

Table VI ‘SCF’ (note a: Werner and Meyer, without vibrational correction): static 2.365.

reinsch_1985/werner_meyer_pno_ci_Ne#

{
  "id": "werner_meyer_pno_ci_Ne",
  "material": "Ne",
  "file": "Ne/reinsch_1985__werner_meyer_pno_ci_Ne.csv",
  "table": "tbl_c3d0b718917c",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "H.-J. Werner and W. Meyer, Mol. Phys. 31, 855 (1976)"
  ]
}

Table VI ‘PNO-CI’ (Werner and Meyer): static 2.616.

reinsch_1985/werner_meyer_cepa_Ne#

{
  "id": "werner_meyer_cepa_Ne",
  "material": "Ne",
  "file": "Ne/reinsch_1985__werner_meyer_cepa_Ne.csv",
  "table": "tbl_c3d0b718917c",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "H.-J. Werner and W. Meyer, Mol. Phys. 31, 855 (1976)"
  ]
}

Table VI ‘CEPA’ (Werner and Meyer): static 2.676.

reinsch_1985/mcscf_CH4#

{
  "id": "mcscf_CH4",
  "material": "CH4",
  "file": "CH4/reinsch_1985__mcscf_CH4.csv",
  "table": "tbl_eecb6e4f851f",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "check"
}

Table V ‘CH4 alpha’ (this work, r_CH = 2.061 bohr, no vibrational averaging), omega = 0-0.30 hartree, 7 points; 9.6 % below ‘Exp’ at omega = 0, 20 % at 0.30.

reinsch_1985/expt_CH4#

{
  "id": "expt_CH4",
  "material": "CH4",
  "file": "CH4/reinsch_1985__expt_CH4.csv",
  "table": "tbl_eecb6e4f851f",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "Landolt-Bornstein, Zahlenwerte und Funktionen, 6. Aufl., Band II/8, S. 6-871 ff."
  ]
}

Table V ‘alpha(Exp)’ (note c: C_1/(nu_1^2 - nu^2) + C_2/(nu_2^2 - nu^2) with values taken from Landolt-Bornstein): the author’s evaluation of a two-term refractivity fit, not measurements; at omega = 0.25-0.30 hartree (182-152 nm) an extrapolation of a fit to longer-wavelength data is likely (the fit’s range is not given). 7 points.

reinsch_1985/werner_meyer_CH4#

{
  "id": "werner_meyer_CH4",
  "material": "CH4",
  "table": "text",
  "quantity": "polarizability",
  "unit": "au",
  "abscissa_unit": "hartree",
  "use": "reproduced",
  "reproduced_from": [
    "H.-J. Werner and W. Meyer, Mol. Phys. 31, 855 (1976)"
  ]
}

2 inline points in the source record.

Table V note f (p. 5790, on the static CH4 value; the note’s wording follows note d, ‘Werner and Meyer (Ref. 5) for omega = 0 PNO-CI/CEPA’): ‘16.39/16.53’. Rows pno_ci and cepa, static.