ward_1984 ========= J\. F\. Ward and D\. S\. Elliott, J\. Chem\. Phys\. 80, 1003 \(1984\) `Source record `__ · :doc:`Catalogue ` · :doc:`Review register ` DOI: `10\.1063/1\.446825 `__ **Source kind:** measurement **Recorded technique:** Third\-harmonic generation of a ruby laser \(694 nm, 1 MW, 40 ns\) focused \(b = 6\.1 mm\) near a glass/gas interface; the harmonic generated in the gas interferes with that of the absorbing glass\. S\(Omega\) measured at ten normalized densities Omega = rho Delta k\_0 b/2 \(0\-1\.5, rho in amagat\), alternating with helium; S\(0\) and S\(infinity\) fitted with the Gaussian\-beam integral Q \(Eqs\. \(4\)\-\(7\)\); binary mixtures fix the sign ambiguity\. **Materials in structured entries:** CH4, SF6 **Dataset quantities:** hyperpolarizability **Contents:** 8 datasets; 0 formulas. Curation notes -------------- THG coefficients of CH4 and SF6 \(and of CH3F, CH2F2, CHF3 and CF4, which are not curated species and are skipped\), compared with dcSHG and Kerr coefficients\. Definitions \(pp\. 1003\-1004\)\: chi is 'the third\-harmonic coefficient' of Ward and New \(Ref\. 1 = ward\_1969\), i\.e\. chi = gamma\_T/6 \(Ward's K = 1/4 for THG, per molecule\)\. Eq\. \(9\)\: chi\_He = 4\.00 x 10^\-39 esu/atom \(Sitz and Yaris\), and Eq\. \(10\)\: chi\_X = chi\_He \(Delta k\_0\)\_X/\(Delta k\_0\)\_He \[1 \- \(S\_X\(inf\)/S\_X\(0\)\)^1/2\]/\[1 \- \(S\_He\(inf\)/S\_He\(0\)\)^1/2\]\: every chi is a measured ratio to helium times 4\.00\. Delta k\_0 = 3w \[n^w\(rho\) \- n^3w\(rho\)\]/\(c rho\) per amagat \(Eq\. \(3\)\) 'are known' \(Ref\. 15, Elliott and Ward, to be published\)\. The comparison columns are dcSHG chi\(\-2w; 0, w, w\) and Kerr chi\(\-w; w, 0, 0\) in the same \(Ward\) convention\: checked for column b, Shelton and Buckingham's gamma \(shelton\_1982 Table II, 10^\-63 C^4 m^4 J^\-3, Taylor\) x 8\.0888e24 / 6 = CH4 334\.6 \(printed 333\), SF6 144\.3 \(144\), CF4 103\.7 \(103\), CHF3 146\.9 \(146\), CH3F 217 \(216\)\. Uncertainties\: the parentheses are in units of the last digit; the text \(p\. 1005\) says the fits' dependence on z\_I = 10 \+\- 2 mm changes chi by 'never more than 5 %'\. Error flags are standard deviations of the mean; the level of Table I's parentheses is not stated\. The sign ambiguity of Ward and New 1969 is resolved \(p\. 1004\)\: q = \-1 for He and SF6 by fit quality and, through mixtures, for all gases here and 'for all gases studied in Ref\. 1' \(Ward and New's set \(i\)\)\. Part\: THG is nearly electronic; the paper \(p\. 1005\) finds chi \> chi\(dcSHG\) \> chi\(Kerr\) for CH4, as electronic dispersion predicts, but not for CF4 and SF6, which 'indicates the existence of significant vibrational contributions' \(Ref\. 13, Elliott and Ward, Mol\. Phys\., to be published\)\. THG values recorded total\. The 694 nm is printed as such \(ruby\)\. **Recorded bibliographic identity status:** VALIDATED\_WITH\_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents. Datasets -------- ward\_1984/thg\_CH4 ~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "thg_CH4", "material": "CH4", "file": "CH4/ward_1984__thg_CH4.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "primary", "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "thg", "convention": "ward_1969", "part": "total", "normalized_to": "He = 4.00e-39 esu (Sitz and Yaris theory)" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column a\: this work's THG chi\(\-3w; w, w, w\) at 694 nm, relative to helium normalized to 4\.00 x 10^\-39 esu \(Eq\. \(9\)\); Ward's convention \(gamma\_T/6\)\. Total \(THG has no rotational part; the vibrational one is not separated\)\. ward\_1984/thg\_SF6 ~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "thg_SF6", "material": "SF6", "file": "SF6/ward_1984__thg_SF6.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "primary", "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "thg", "convention": "ward_1969", "part": "total", "normalized_to": "He = 4.00e-39 esu (Sitz and Yaris theory)" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column a\: this work's THG chi\(\-3w; w, w, w\) at 694 nm, relative to helium normalized to 4\.00 x 10^\-39 esu \(Eq\. \(9\)\); Ward's convention \(gamma\_T/6\)\. Total \(THG has no rotational part; the vibrational one is not separated\)\. ward\_1984/dcshg\_miller\_ward\_CH4 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "dcshg_miller_ward_CH4", "material": "CH4", "file": "CH4/ward_1984__dcshg_miller_ward_CH4.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "reproduced", "reproduced_from": [ "C. K. Miller and J. F. Ward, Phys. Rev. A 16, 1179 (1977)" ], "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "eshg", "convention": "ward_1969", "part": "total" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column chi\(dcSHG\), note c \(Ref\. 5, Miller and Ward 1977, 694 nm\)\. Ward's convention \(gamma\_T/6\)\. Part as the original \(ESHG\: electronic plus a small vibrational part\)\: total\. ward\_1984/dcshg\_ward\_miller\_SF6 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "dcshg_ward_miller_SF6", "material": "SF6", "file": "SF6/ward_1984__dcshg_ward_miller_SF6.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "reproduced", "reproduced_from": [ "ward_1979" ], "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "eshg", "convention": "ward_1969", "part": "total" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column chi\(dcSHG\), note f \(Ref\. 6, Ward and Miller 1979, 694 nm\)\: the same 130\(2\) as ward\_1979 chi3\_SF6\. Ward's convention \(gamma\_T/6\)\. Part as the original \(ESHG\: electronic plus a small vibrational part\)\: total\. ward\_1984/dcshg\_shelton\_buckingham\_CH4 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "dcshg_shelton_buckingham_CH4", "material": "CH4", "file": "CH4/ward_1984__dcshg_shelton_buckingham_CH4.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "reproduced", "reproduced_from": [ "shelton_1982" ], "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "eshg", "convention": "ward_1969", "part": "total" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column chi\(dcSHG\) b \(Ref\. 7, Shelton and Buckingham 1982, printed '541 nm', corrected to 514\.5 nm by an erratum\)\: Shelton and Buckingham's gamma divided by 6 \(see the source notes\)\. Ward's convention \(gamma\_T/6\)\. Part as the original \(ESHG\: electronic plus a small vibrational part\)\: total\. ward\_1984/dcshg\_shelton\_buckingham\_SF6 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "dcshg_shelton_buckingham_SF6", "material": "SF6", "file": "SF6/ward_1984__dcshg_shelton_buckingham_SF6.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "reproduced", "reproduced_from": [ "shelton_1982" ], "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "eshg", "convention": "ward_1969", "part": "total" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column chi\(dcSHG\) b \(Ref\. 7, Shelton and Buckingham 1982, printed '541 nm', corrected to 514\.5 nm by an erratum\)\: Shelton and Buckingham's gamma divided by 6 \(see the source notes\)\. Ward's convention \(gamma\_T/6\)\. Part as the original \(ESHG\: electronic plus a small vibrational part\)\: total\. ward\_1984/kerr\_buckingham\_orr\_CH4 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "kerr_buckingham_orr_CH4", "material": "CH4", "file": "CH4/ward_1984__kerr_buckingham_orr_CH4.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "reproduced", "reproduced_from": [ "A. D. Buckingham and B. J. Orr, Trans. Faraday Soc. 65, 673 (1969)" ], "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "dc_kerr", "convention": "ward_1969", "part": "unknown" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column chi\(Kerr\), note d \(Ref\. 3, Buckingham and Orr 1969, 633 nm\)\. Ward's convention \(gamma\_T/6\)\. Part as measured \(Kerr of a tetrahedral/octahedral molecule\: no orientational term, but the vibrational part is included; not stated\)\: unknown\. ward\_1984/kerr\_buckingham\_dunmur\_SF6 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "id": "kerr_buckingham_dunmur_SF6", "material": "SF6", "file": "SF6/ward_1984__kerr_buckingham_dunmur_SF6.csv", "table": "tbl_67cee6b847af", "quantity": "hyperpolarizability", "unit": "esu", "scale": 1e-39, "abscissa_unit": "nm", "use": "reproduced", "reproduced_from": [ "buckingham_1968" ], "uncertainty": { "column": true, "level": "not stated" }, "parameters": { "process": "dc_kerr", "convention": "ward_1969", "part": "unknown" } } Table I \(p\. 1004\), chi x 10^39 \(esu/molecule\), column chi\(Kerr\), note g \(Ref\. 2, Buckingham and Dunmur 1968, 633 nm\)\: their gamma 1\.2 \+\- 0\.1 x 10^\-36 esu / 6 = 200 \+\- 17 \(printed 200\(16\)\)\. Ward's convention \(gamma\_T/6\)\. Part as measured \(Kerr of a tetrahedral/octahedral molecule\: no orientational term, but the vibrational part is included; not stated\)\: unknown\. Formulas -------- No formulas are recorded. Corrections ----------- .. code-block:: text [ { "dataset": "dcshg_shelton_buckingham_CH4", "row": "chi", "column": "x", "printed": "541", "corrected": "514.5", "reason": "Table I footnote b prints 'Reference 7, 541 nm' (page image checked); Reference 7 (Shelton and Buckingham, Phys. Rev. A 26, 2787 (1982)) measured its hyperpolarizabilities at 514.5 nm (its Table II caption), and its gamma values divided by 6 reproduce this column (CH4 248.2e-63 -> 334.6, SF6 107e-63 -> 144.3, x 10^-39 esu with 8.0888e24 esu per SI unit): 541 is a transposition of 514.", "evidence": "shelton_1982, Table II (tbl_09cd9a18fa27): 'Hyperpolarizabilities and phase-matching densities of several molecules, measured at 514.5 nm'; the conversion checked 2026-09-26." }, { "dataset": "dcshg_shelton_buckingham_SF6", "row": "chi", "column": "x", "printed": "541", "corrected": "514.5", "reason": "Table I footnote b prints 'Reference 7, 541 nm' (page image checked); Reference 7 (Shelton and Buckingham, Phys. Rev. A 26, 2787 (1982)) measured its hyperpolarizabilities at 514.5 nm (its Table II caption), and its gamma values divided by 6 reproduce this column (CH4 248.2e-63 -> 334.6, SF6 107e-63 -> 144.3, x 10^-39 esu with 8.0888e24 esu per SI unit): 541 is a transposition of 514.", "evidence": "shelton_1982, Table II (tbl_09cd9a18fa27): 'Hyperpolarizabilities and phase-matching densities of several molecules, measured at 514.5 nm'; the conversion checked 2026-09-26." } ] Formula corrections, where recorded, appear with their formulas above. Curation notes may also discuss corrections or unresolved interpretation. Consult the :doc:`review register ` for the checks and decisions.