rosasco_1986#

G. J. Rosasco and W. S. Hurst, J. Opt. Soc. Am. B 3, 1251 (1986)

Source record · Catalogue · Review register

DOI: 10.1364/josab.3.001251

Source kind: measurement

Recorded technique: cw phase-modulated stimulated Raman spectroscopy (optical-heterodyne-detected Raman-induced Kerr effect) as in rosasco_1985: Kr-ion pump (14779 cm^-1, 10 MHz), ring-dye probe (17751 cm^-1, 1 MHz), 45-pass cell; 5 % D2 in H2 (the D2 Q(3), Q(4) lines as internal standard) at 1.0-6.0 atm, bracketed by two 5 % D2 in He runs that calibrate the mirror contribution; ideal-gas densities, pressure and temperature to 0.1 %.

Materials in structured entries: D2, H2, He

Dataset quantities: nonlinear_susceptibility

Contents: 5 datasets; 0 formulas.

Curation notes#

The electronic hyperpolarizability of H2 from its nonresonant optical (ac) Kerr constant, and a dispersion comparison of H2’s electronic hyperpolarizability from ac Kerr, dc Kerr, THG, FISHG and CARS (Fig. 4, figure only).

Definitions (Appendix A, p. 1255): (A1) P_1,i = D chi_ijkl(-w1, w2, w3, w4) E_2,j E_3,k E_4,l with D = 6, 3, 1 and Fourier components (as rosasco_1985); (A2) Hellwarth’s representation 24 chi_ijkl = [sigma + 2A + B + B] delta delta + ...; sigma the electronic hyperpolarizability, A and B the nuclear (vibrational, rotational) terms, (A3)-(A10); the measured nonresonant chi^N = 2 sigma/24 + 2 B(0)/24 + chi_R(2A+B)^OR (Eq. (6)), with the far-off-resonance Raman sums (A12) and the reorientation term (A13) 2B(0)/24 = (2/24) (1/15) (N/k_B T) gamma_0^2 (1 - R_0 + 8 R_0^2/15 + ...), gamma_0 the optical polarizability anisotropy (Bridge and Buckingham 1966, not in the library). Eq. (11), p. 1253: ‘[3 sigma/24]_1 amagat, cgs = N0 gamma/24 = 5.639 x 10^-22 gamma_AU’ with gamma in atomic units (checked: 2.687e19/24 x 5.0367e-40 esu/au = 5.639e-22), gamma the Taylor (Shelton) gamma. So gamma_T (au) = (3 sigma/24)/5.639e-22 = 1.5 (2 sigma/24)/5.639e-22.

Result (p. 1253): chi_0^N/(A_0 N_0) = 0.0137 (+0.0003, -0.0005) (Eq. (7), the range from the mirror model), A_0 N_0 = 461.4 x 10^-19 esu (rosasco_1985 Eq. (47)); with the computed 2B(0)/24 and off-resonant Raman terms of Table 1 this gives 2 sigma/24 = 2.966 x 10^-19 esu for H2. (Recomputing chi_0^N from Table 1’s components, 2.966 + 2.722 + 0.665 - 0.00547 = 6.348 x 10^-19 = 0.01376 A_0 N_0, which rounds to 0.0138, not the printed 0.0137: a rounding question only.) The reference susceptibility ‘is believed to have an uncertainty of +-5 %’ (p. 1251); Table 1 note a: ‘Estimated errors for most of the values given in this table are +-5 %. These results assume the pump (14779 cm^-1) and probe (17751 cm^-1) frequencies employed in this work.’

Table 1 rows not extracted (computed corrections, a mixture of the A and B terms, not one ‘part’): chi_R(2A+B)^OR sums H2 0.665 (Sum’ over omega - Omega, excluding the resonant Q branch) and -0.00547 (omega + Omega), D2 0.0834 and -0.00275; chi_R(2A-B)^OR sums H2 0.663 and +0.00471, D2 0.0516 and +0.00243 (the last row prints B(omega - Omega) inside a sum over omega + Omega, image checked: presumably a misprint; the H2 0.663 cell carries a stray prime on its footnote f); A_0 N_0 (D2) 461.4.

Dispersion (pp. 1253-1254): Owyoung’s and Hellwarth’s chi^NRE(-w1, w2, w3, w4) proportional to chi(w1) chi(w2) chi(w3) chi(w4) (Eq. (8)), with one pole: chi^NRE proportional to chi_0 [1 + k (w^2)_eff] (Eq. (9)), (w^2)_eff = w1^2 + w2^2 + w3^2 + w4^2 (Eq. (10)); dc Kerr, FISHG and THG dispersion rates in the ratio 1:3:6 (Dawes, Finn). No coefficients are given (the Fig. 4 line is Mizrahi and Shelton’s): no formula recorded. In Fig. 4 the dc-KE value of rosasco_1985 Table IV is corrected by +3 % for far-off-resonance Raman terms, the CARS value is Lundeen et al.’s D2 scaled by Mizrahi and Shelton’s H2:D2 ratio, the THG value Ward and New’s; the paper speculates the dc Kerr value ‘may be approximately 20 % low’.

Wavelengths: the pump is given as 14779 cm^-1 (vacuum wavenumber, as printed; the Kr-ion 676.4 nm line), recorded with wavelength_unit cm-1; the probe 17751 cm^-1 is in parameters.

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

Datasets#

rosasco_1986/sigma_H2#

{
  "id": "sigma_H2",
  "material": "H2",
  "file": "H2/rosasco_1986__sigma_H2.csv",
  "table": "tbl_1142277dccf1",
  "quantity": "nonlinear_susceptibility",
  "unit": "esu (per amagat)",
  "scale": 1e-19,
  "abscissa_unit": "cm-1",
  "use": "primary",
  "uncertainty": {
    "relative": 0.05,
    "level": "not stated"
  },
  "parameters": {
    "process": "kerr",
    "convention": "rosasco_1985_hellwarth",
    "part": "electronic",
    "probe_cm1": 17751
  }
}

Table 1 (p. 1254), 10^-19 esu at 1 amagat and 296 K (per amagat, N0 = Loschmidt’s number; no state), Hellwarth’s convention of rosasco_1985 (2 sigma/24 = N0 gamma_T/36): 2 sigma/24 of H2, ‘determined in this work’ (note b): the electronic part of the measured ac Kerr constant, chi_0^N minus the computed 2B(0)/24 (2.722) and off-resonant Raman terms. Nondegenerate optical Kerr chi(-w, w, W, -W), pump 14779 cm^-1, probe 17751 cm^-1. +-5 % (note a; the level is not stated). Electronic (the paper: ‘the electronic hyperpolarizability’), separated by subtraction of the calculated reorientation and Raman terms.

rosasco_1986/sigma_D2#

{
  "id": "sigma_D2",
  "material": "D2",
  "file": "D2/rosasco_1986__sigma_D2.csv",
  "table": "tbl_1142277dccf1",
  "quantity": "nonlinear_susceptibility",
  "unit": "esu (per amagat)",
  "scale": 1e-19,
  "abscissa_unit": "cm-1",
  "use": "check",
  "parameters": {
    "process": "kerr",
    "convention": "rosasco_1985_hellwarth",
    "part": "electronic",
    "probe_cm1": 17751
  }
}

Table 1 (p. 1254), 10^-19 esu at 1 amagat and 296 K (per amagat, N0 = Loschmidt’s number; no state), Hellwarth’s convention of rosasco_1985 (2 sigma/24 = N0 gamma_T/36): 2 sigma/24 of D2, ‘From the H2 value and the ratio of H2/D2 of ~1.02; see Ref. 13’ (note c, Mizrahi and Shelton 1985, mizrahi_1985_h2d2): derived, not measured (2.966/1.02 = 2.908). Electronic.

rosasco_1986/sigma_He#

{
  "id": "sigma_He",
  "material": "He",
  "file": "He/rosasco_1986__sigma_He.csv",
  "table": "tbl_1142277dccf1",
  "quantity": "nonlinear_susceptibility",
  "unit": "esu (per amagat)",
  "scale": 1e-19,
  "abscissa_unit": "cm-1",
  "use": "reproduced",
  "reproduced_from": [
    "rosasco_1985",
    "ward_1969"
  ],
  "parameters": {
    "process": "kerr",
    "convention": "rosasco_1985_hellwarth",
    "part": "electronic"
  }
}

Table 1 (p. 1254), 10^-19 esu at 1 amagat and 296 K (per amagat, N0 = Loschmidt’s number; no state), Hellwarth’s convention of rosasco_1985 (2 sigma/24 = N0 gamma_T/36): 2 sigma/24 of He, ‘Value from Ref. 14 [Ward and New], as reported in Ref. 6 [rosasco_1985]’ (note d): 1.5 x 0.178 = 0.267 = rosasco_1985’s He reference (0.0267 x 10^-18) in 3 sigma/24; ultimately the Sitz and Yaris theory Ward and New normalize to. Used to model the D2:He calibration runs. Electronic. The wavelength column holds this paper’s pump (the value’s own frequency is Ward and New’s).

rosasco_1986/reorientation_H2#

{
  "id": "reorientation_H2",
  "material": "H2",
  "file": "H2/rosasco_1986__reorientation_H2.csv",
  "table": "tbl_1142277dccf1",
  "quantity": "nonlinear_susceptibility",
  "unit": "esu (per amagat)",
  "scale": 1e-19,
  "abscissa_unit": "cm-1",
  "use": "check",
  "parameters": {
    "process": "kerr",
    "convention": "rosasco_1985_hellwarth",
    "part": "rotational",
    "temperature_k": 296
  }
}

Table 1 (p. 1254), 10^-19 esu at 1 amagat and 296 K (per amagat, N0 = Loschmidt’s number; no state), Hellwarth’s convention of rosasco_1985 (2 sigma/24 = N0 gamma_T/36): 2B(0)/24 of H2 = 2.722, the molecular-reorientation (orientational) term of the ac Kerr constant, ‘Calculated from Eq. (A13) and the anisotropy values from Ref. 8’ (Bridge and Buckingham 1966; note e), at 296 K (it scales as 1/T). Computed, not measured. Rotational.

rosasco_1986/reorientation_D2#

{
  "id": "reorientation_D2",
  "material": "D2",
  "file": "D2/rosasco_1986__reorientation_D2.csv",
  "table": "tbl_1142277dccf1",
  "quantity": "nonlinear_susceptibility",
  "unit": "esu (per amagat)",
  "scale": 1e-19,
  "abscissa_unit": "cm-1",
  "use": "check",
  "parameters": {
    "process": "kerr",
    "convention": "rosasco_1985_hellwarth",
    "part": "rotational",
    "temperature_k": 296
  }
}

Table 1 (p. 1254), 10^-19 esu at 1 amagat and 296 K (per amagat, N0 = Loschmidt’s number; no state), Hellwarth’s convention of rosasco_1985 (2 sigma/24 = N0 gamma_T/36): 2B(0)/24 of D2 = 2.827, the molecular-reorientation (orientational) term of the ac Kerr constant, ‘Calculated from Eq. (A13) and the anisotropy values from Ref. 8’ (Bridge and Buckingham 1966; note e), at 296 K (it scales as 1/T). Computed, not measured. Rotational.

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.