rice_1991#
J. E. Rice, P. R. Taylor, T. J. Lee and J. Almlof, “The determination of accurate dipole polarizabilities alpha and gamma for the noble gases”, J. Chem. Phys. 94, 4972 (1991)
Source record · Catalogue · Review register
DOI: 10.1063/1.460533
Source kind: theory
Recorded technique: Finite-field SCF, MP2, CCSD and CCSD(T) energies of He-Xe in large ANO basis sets with diffuse spdf(g) extensions (Sec. II, pp. 4973-4974); fields 0-0.020 a.u., the energies fitted to a polynomial with terms above fourth order; core correlation by MP2 (and CCSD for Ar); a first-order (mass-velocity + Darwin) relativistic correction at the SCF level for Kr and Xe. Static values only.
Materials in structured entries: Ar, He, Kr, Ne, Xe
Dataset quantities: hyperpolarizability
Contents: 16 datasets; 0 formulas.
Curation notes#
Identity: pdf page 1 is the publisher’s cover; journal pages 4972-4979 = pdf pages 2-9. Page numbers below are journal pages.
DEFINITION AND CONVENTION (p. 4973): ‘E(F) = E_0 - (1/2) alpha F^2 - (1/24) gamma F^4 ...’ for an atom in an S state in a static field F, following Buckingham. gamma is the fourth field derivative of the energy: the static limit of the Taylor-series (T) convention of Shelton and Rice. Process static, part electronic (atoms), nonrelativistic except the rows marked [relativistic]. Atomic units (no conversion stated). Fitting error ‘no more than 0.5 %’ (p. 4974): ‘we quote krypton and xenon hyperpolarizabilities to three figures only’.
BEST ESTIMATES (Table VI, p. 4978, image checked; datasets best_*): He 43.6 (CCSD = full CI in basis B, Table V; ‘Our best estimate of gamma for helium is 43.6 a.u.’, 1 % above Bishop and Pipin’s 43.104 printed in parentheses, which is bishop_1989 and not taken again); Ar 1220 +- 30 (valence CCSD(T) 1234 +- 5 +- 6 +- 5, core correlation -12 by CCSD with its whole size as uncertainty, p. 4975); Kr 2810 +- 90 (p. 4976: core 40, valence correlation and relativity 30, basis 20); Xe 7030 +- 200 in Table VI, but the text gives ‘our predicted gamma for xenon is 7020 +- 200 a.u.’ (p. 4977): 7030 excludes and 7020 includes the -10 a.u. relativistic correction (p. 4976); the table’s 7030 is recorded, the difference noted (TC-243). The uncertainties are the authors’ estimates (‘the computed alpha and gamma values are estimated to be accurate to within a few percent’, abstract); their level is not stated.
NEON (Table IV, ‘Taken from Ref. 3 (MP2 result is from this work)’, and the best estimate 119 +- 4): Ref. 3 is Taylor, Lee, Rice and Almlof, Chem. Phys. Lett. 163, 359 (1989), whose neon values were later revised by an erratum, Chem. Phys. Lett. 189, 197 (1992) (cited by rice_1992, Ref. 2, and by Shelton and Rice 1994, Ref. 110): the corrected CCSD(T) value in the same basis is 111.0 and the best estimate 110 +- 3 (rice_1992_neon, Table 1 and p. 7 of the manuscript). The Table IV rows from Ref. 3 and the best estimate 119 +- 4 are therefore kept but EXCLUDED; the MP2 row (110.8, this paper’s) agrees with the revised work (110.7) and is kept.
RATIOS (Table VI): gamma/gamma_He theory 2.73 (2.76), 28.0 (28.3), 64.2 (65.0), 161 (163) for Ne, Ar, Kr, Xe (in parentheses relative to 43.104) and gamma/gamma_Ar theory 2.30 (Kr), 5.75 (Xe): quotients of the tabulated gammas (checked: 119/43.6 = 2.73, 1220/43.104 = 28.3, 2810/1220 = 2.30, 7030/1220 = 5.76), not recorded as datasets. The experimental ratios 2.76, 2.34, 27.1, 25.5, 60.3, 160 (He) and 2.23, 5.90 (Ar) are the reproduced gammas over 43.104 or over 1167 (2600/1167 = 2.23, 6888/1167 = 5.90): not recorded either. The text adds (p. 4978): ‘At the lowest frequency for which experimental measurements were made, the ratio gamma_Ar : gamma_He is 27.84 +- 0.16. Extrapolation to zero frequency reduces this ratio by 3 % to 27.07’ (Shelton 1990).
REPRODUCED EXPERIMENTAL VALUES (Table VI ‘gamma expt.’): footnote d, Shelton, Phys. Rev. A 42, 2578 (1990) = shelton_1990 (Ne 119 +- 2, later revised by Shelton to 108 +- 2, see rice_1992_neon; Ar 1167 +- 6; Kr 2600; Xe 6888); footnote f, Buckingham and Dunmur, Trans. Faraday Soc. 64, 1987 (1968) as printed (the library’s buckingham_1968 is Trans. Faraday Soc. 64, 1776 (1968), ‘Kerr effect in inert gases and sulphur hexafluoride’, which rice_1992_neon cites as 64, 1776: the page 1987 is a misprint of the reference, probably), Ne 101 +- 8, a dc Kerr value at 632.8 nm (rice_1992, p. 7586), not a static value; footnote g, Mizrahi and Shelton, Phys. Rev. Lett. 55, 696 (1985) = mizrahi_1985_arn2o2, Ar 1101 +- 8. The text also quotes Shelton’s earlier static Ar estimate 1108 (Ref. 20) revised to 1167 +- 6 (p. 4975).
Not extracted: the alpha columns (linear data, for the linear phase: SCF, MP2, CCSD, CCSD(T) and best estimates He 1.384, Ne 2.63 +- 0.03 in Table VI but 2.69 +- 0.03 in the text (p. 4977), Ar 11.2 +- 0.1 (text 11.17 +- 0.05), Kr 17.0 +- 0.2, Xe 27.4 +- 0.5 (text 27.4 +- 0.8); the Kumar and Meath experimental alphas).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
rice_1991/methods_He#
{
"id": "methods_He",
"material": "He",
"file": "He/rice_1991__methods_He.csv",
"table": "tbl_39e1e26d258b",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table V: static gamma by basis set (ANO bases A, B, C of the footnotes, with diffuse sets) and method; row id ‘<basis> <method>’. CCSD is full CI for two electrons (p. 4977). Valence correlation unless marked.
rice_1991/methods_Ne#
{
"id": "methods_Ne",
"material": "Ne",
"file": "Ne/rice_1991__methods_Ne.csv",
"table": "tbl_3fc8a4dd7268",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table IV, MP2 in basis B + (3s3p2d 3f): ‘MP2 result is from this work’ (footnote a). Static gamma; row id ‘<basis> <method>’.
rice_1991/methods_taylor_Ne#
{
"id": "methods_taylor_Ne",
"material": "Ne",
"file": "Ne/rice_1991__methods_taylor_Ne.csv",
"table": "tbl_3fc8a4dd7268",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "excluded",
"reproduced_from": [
"P. R. Taylor, T. J. Lee, J. E. Rice and J. Almlof, Chem. Phys. Lett. 163, 359 (1989), before its erratum Chem. Phys. Lett. 189, 197 (1992)"
],
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
EXCLUDED. Table IV rows ‘Taken from Ref. 3’ (Taylor et al., Chem. Phys. Lett. 163, 359 (1989)), revised by that paper’s erratum (Chem. Phys. Lett. 189, 197 (1992)): e.g. CCSD(T) 118.3 here against 111.0 in the same basis after the revision (rice_1992_neon). Rows ‘ [core]’: 10 electrons correlated.
rice_1991/methods_Ar#
{
"id": "methods_Ar",
"material": "Ar",
"file": "Ar/rice_1991__methods_Ar.csv",
"table": "tbl_6788c2ece063",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table I: static gamma by basis set (ANO bases A, B, C of the footnotes, with diffuse sets) and method; row id ‘<basis> <method>’. Rows ‘ [core]’: 16 electrons correlated (L shell). Valence correlation unless marked.
rice_1991/methods_Kr#
{
"id": "methods_Kr",
"material": "Kr",
"file": "Kr/rice_1991__methods_Kr.csv",
"table": "tbl_7b5b5d1dda56",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table II: static gamma by basis set (ANO bases A, B, C of the footnotes, with diffuse sets) and method; row id ‘<basis> <method>’. Rows ‘ [core]’: 26 electrons correlated; ‘ [relativistic]’: SCF with the first-order mass-velocity + Darwin correction (compare the plain SCF row 2260). Valence correlation unless marked.
rice_1991/methods_Xe#
{
"id": "methods_Xe",
"material": "Xe",
"file": "Xe/rice_1991__methods_Xe.csv",
"table": "tbl_d0c6f1d5dee5",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table III: static gamma by basis set (ANO bases A, B, C of the footnotes, with diffuse sets) and method; row id ‘<basis> <method>’. Rows ‘ [core]’: 26 electrons correlated; ‘ [relativistic]’: SCF with the first-order mass-velocity + Darwin correction (compare 5870). Valence correlation unless marked.
rice_1991/best_He#
{
"id": "best_He",
"material": "He",
"file": "He/rice_1991__best_He.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma^a theory’: the best estimate 43.6 (CCSD = full CI, basis B + (3s2p2d 2f)); no uncertainty printed. Superseded by bishop_1989 (43.104), which the authors quote.
rice_1991/best_Ne#
{
"id": "best_Ne",
"material": "Ne",
"file": "Ne/rice_1991__best_Ne.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "excluded",
"reproduced_from": [
"P. R. Taylor, T. J. Lee, J. E. Rice and J. Almlof, Chem. Phys. Lett. 163, 359 (1989), before its erratum Chem. Phys. Lett. 189, 197 (1992)"
],
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
EXCLUDED. Table VI best estimate 119 (+- 4) from Ref. 3 before its erratum; revised to 110 +- 3 (rice_1992_neon).
rice_1991/best_Ar#
{
"id": "best_Ar",
"material": "Ar",
"file": "Ar/rice_1991__best_Ar.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma^a theory’ best estimate 1220 (+- 30): valence CCSD(T) 1234 with basis and triples additivity, core correlation -12 by CCSD (uncertainty 12), p. 4975. Uncertainty: the authors’ estimate, level not stated.
rice_1991/best_Kr#
{
"id": "best_Kr",
"material": "Kr",
"file": "Kr/rice_1991__best_Kr.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma^a theory’ best estimate 2810 (+- 90), p. 4976. Uncertainty: the authors’ estimate, level not stated.
rice_1991/best_Xe#
{
"id": "best_Xe",
"material": "Xe",
"file": "Xe/rice_1991__best_Xe.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma^a theory’ best estimate 7030 (+- 200); the text’s final value is 7020 +- 200 including the -10 a.u. relativistic correction (p. 4977): see the source notes. Uncertainty: the authors’ estimate, level not stated.
rice_1991/expt_Ne#
{
"id": "expt_Ne",
"material": "Ne",
"file": "Ne/rice_1991__expt_Ne.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"shelton_1990"
],
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma expt.’, footnote d (Shelton, Phys. Rev. A 42, 2578 (1990)): the static value extrapolated from ESHG, 119 +- 2, later revised by Shelton to 108 +- 2 (rice_1992_neon).
rice_1991/expt_dc_kerr_Ne#
{
"id": "expt_dc_kerr_Ne",
"material": "Ne",
"file": "Ne/rice_1991__expt_dc_kerr_Ne.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"buckingham_1968"
],
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"process": "dc_kerr",
"convention": "T",
"part": "electronic",
"component": "K"
}
}
Table VI ‘gamma expt.’, footnote f (Buckingham and Dunmur 1968): 101 +- 8, a dc Kerr gamma^K at 632.8 nm (the wavelength and process from rice_1992, p. 7586, and rice_1992_neon; Table VI lists it beside the static values).
rice_1991/expt_Ar#
{
"id": "expt_Ar",
"material": "Ar",
"file": "Ar/rice_1991__expt_Ar.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"shelton_1990",
"mizrahi_1985_arn2o2"
],
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma expt.’: row ‘Ar^d’ 1167 +- 6 (Shelton 1990, static extrapolation of ESHG), row ‘Ar^g’ 1101 +- 8 (Mizrahi and Shelton 1985).
rice_1991/expt_Kr#
{
"id": "expt_Kr",
"material": "Kr",
"file": "Kr/rice_1991__expt_Kr.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"shelton_1990"
],
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma expt.’, footnote d: 2600 (Shelton 1990), no uncertainty printed.
rice_1991/expt_Xe#
{
"id": "expt_Xe",
"material": "Xe",
"file": "Xe/rice_1991__expt_Xe.csv",
"table": "tbl_ff5895bcf9bb",
"quantity": "hyperpolarizability",
"unit": "au",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"shelton_1990"
],
"parameters": {
"process": "static",
"convention": "T",
"part": "electronic"
}
}
Table VI ‘gamma expt.’, footnote d: 6888 (Shelton 1990), no uncertainty printed.
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.