sharipov_2017#
A. S. Sharipov, B. I. Loukhovitski, and A. M. Starik, “The influence of vibrations of polyatomic molecules on dipole moment and static dipole polarizability: theoretical study”, J. Phys. B: At. Mol. Opt. Phys. 50, 165101 (2017)
Source record · Catalogue · Review register
Source kind: theory
Recorded technique: Density-functional (B97-2/Sadlej pVTZ; aug-cc-pVTZ for atoms the Sadlej set lacks) potential-energy, dipole-moment and polarizability surfaces along each normal mode (harmonic normal modes; rectilinear displacements; modes as independent 1D oscillators, degenerate modes treated separately; rotation ignored), 1D Schroedinger equations solved by Numerov’s method for levels below 10 000 cm^-1; finite-field polarizabilities (field 1e-3 au) averaged over the vibrational wave functions without (‘unperturbed potential’, UP) and with (‘perturbed potential’, PP) the field’s effect on the potential. The electronic polarizability alpha_e at the equilibrium geometry also by finite-field MP4(SDQ)/Sadlej//B97-2/Sadlej (MP4(SDTQ) where marked a) (pp. 3-5, Firefly/GAMESS).
Materials in structured entries: CH4, CO2, O3, SF6
Dataset quantities: polarizability
Contents: 4 datasets; 0 formulas.
Curation notes#
Page numbers are the library pdf pages (pdf page 1 is the publisher’s cover). Units: Angstrom^3 (polarizability volumes). Curated species in the paper: CO2, O3, CH4, SF6 (no N2O, N2, O2, H2; the diatomics’ corrections are the authors’ earlier paper, Ref. 36, Loukhovitski et al. 2016, not in the library). H2O and the other 46 species are skipped.
THE DECOMPOSITION (Eqs. 9-12, p. 4): alpha(omega = 0) = alpha_e + Delta alpha^ZPV + Delta alpha^PV (Eq. 11) for a static field; alpha(omega) = alpha_e + Delta alpha^ZPV for omega > 0.05 au, the UV-visible (Eq. 12), ‘the pure vibrational contribution goes to zero’. alpha_e is the clamped-nucleus electronic polarizability at the equilibrium geometry, Delta alpha^ZPV the zero-point vibrational averaging correction (Eq. 9), Delta alpha^PV the pure vibrational polarizability, the infrared-active modes’ static response (Eq. 10); ‘the Delta alpha^PV value can be estimated as a difference between the polarizability obtained from the measurements of dielectric permittivity and refractive index’ (p. 4). Rotation (orientation) is ignored. The thermal population of excited vibrational levels adds Delta alpha^UP(T) = bT + cT^2 (Eq. 18; Table A1’s b, c).
EXTRACTED: alpha_e(MP4) of CO2, O3, CH4, SF6 (Table A1), electronic only, static, equilibrium geometry, no vibrational averaging: ‘check’ datasets (DFT-geometry MP4, no stated accuracy; ‘the present computational strategy overestimates slightly the low-temperature values of polarizability of CO2 and CH4 (by 1 % and 0.3 %)’, p. 12).
NOT EXTRACTED (no quantity for a vibrational correction; a format need), Table A1 (pp. 14-15; images checked), Angstrom^3, alpha_e(B97-2) / alpha_e(MP4) / ZPV / PV / b x 10^6 (A^3/K) / c x 10^9 (A^3/K^2): CO2 2.531 / 2.611 / 0.017 / 0.312 / 12.24 / 2.66 O3 2.727 / 2.801 (MP4(SDTQ)) / 0.013 / 0.312 (Table 2: 0.208, see below) / 5.25 / 2.03 CH4 2.507 / 2.464 / 0.099 / 0.035 / 10.05 / 12.72 SF6 4.682 / 4.665 / 0.023 / 1.893 / 38.18 / 5.43 In atomic units (1 au = 0.148184711 A^3): pure vibrational PV = CO2 2.106, CH4 0.236, SF6 12.77, O3 2.106 (Table A1) or 1.404 (Table 2); ZPV = CO2 0.115, CH4 0.668, SF6 0.155, O3 0.088; Delta alpha^UP(296 K) = CO2 0.026, CH4 0.028, SF6 0.080, O3 0.012 au (computed here from b, c).
Table 2 (p. 9; image checked) repeats ZPV and PV (‘This work’) and lists other works’ values (A^3), reproduced here for the record: CO2 ZPV 0.004 [Bulanin et al. 1988], PV 0.26 [Bishop and Cheung 1982], 0.289 [Bishop and Kirtman 1991], 0.323 [Hohm 2013]; O3 ZPV 0.216, PV 0.209 [Naves et al. 2011]; CH4 ZPV 0.123 [Raynes et al. 1988], 0.123 [Marti et al. 1993], 0.130 [Russell and Spackman 1995], 0.133 [Kongsted and Christiansen 2007], PV 0.034 [Hohm 2013], 0.041 [Kongsted and Christiansen 2007], 0.04 [Pederson et al. 2005]; SF6 PV 2.035 [Hohm 2013], 2.29 [Pederson et al. 2005]. (Hohm 2013’s and Bishop and Cheung’s values are ‘from the measured intensities of the molecule’s infrared-active bands’, p. 9.)
O3’s PV: Table A1 prints 0.312 (the same digits as the CO2 row above it), Table 2 0.208 ‘This work’; one is misprinted, probably Table A1’s (a copy of the CO2 row); not corrected, since neither is extracted (TC-153). The authors themselves call their O3 treatment inadequate (multireference ground state; ZPV 15 times below Naves et al.’s coupled-cluster value, p. 9).
Also not extracted: Table 1 and Appendix B (dipole moments), the figures, the parameters of the approximation formulas (Eqs. 14, 16: p0 = 36.88, p1 = -0.73, p2 = 1.33, p3 = 85.07, p4 = -1.50, p5 = 5.31, p6 = 4.72 D, p7 = 2.16; p. 11), and the supplementary material (PP temperature coefficients, state-specific values; not in the library). Fig. 12’s experimental CH4 and CO2 points (Hohm and Kerl 1990; Kerl et al. 1992) were corrected to static by a TDDFT factor 0.9813 at 633 nm (0.9750 at 546 nm, p. 12).
Recorded bibliographic identity status: VALIDATED. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
sharipov_2017/alpha_e_mp4_CO2#
{
"id": "alpha_e_mp4_CO2",
"material": "CO2",
"file": "CO2/sharipov_2017__alpha_e_mp4_CO2.csv",
"table": "tbl_6536153eecc8",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "check"
}
Table A1 alpha_e(MP4) = 2.611 A^3 (17.62 au): static electronic, clamped nuclei at the B97-2 equilibrium geometry; without ZPV (0.017), the pure vibrational PV (0.312) and the thermal Delta alpha^UP. No uncertainty stated.
sharipov_2017/alpha_e_mp4_O3#
{
"id": "alpha_e_mp4_O3",
"material": "O3",
"file": "O3/sharipov_2017__alpha_e_mp4_O3.csv",
"table": "tbl_6536153eecc8",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "check"
}
Table A1 alpha_e(MP4) = 2.801 A^3 (18.90 au), mark a: MP4(SDTQ) (triple substitutions included). Static electronic, clamped nuclei; the authors’ DFT treatment of O3 is poor (multireference ground state, p. 9). No uncertainty stated.
sharipov_2017/alpha_e_mp4_CH4#
{
"id": "alpha_e_mp4_CH4",
"material": "CH4",
"file": "CH4/sharipov_2017__alpha_e_mp4_CH4.csv",
"table": "tbl_5c6a04a7a846",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "check"
}
Table A1 alpha_e(MP4) = 2.464 A^3 (16.63 au): static electronic, clamped nuclei; the zero-point correction is large for CH4 (ZPV 0.099 A^3 = 0.668 au), so alpha_e + ZPV = 2.563 A^3 (17.30 au) is the comparable optical-limit value (Eq. 12). PV 0.035 A^3 (0.236 au). No uncertainty stated.
sharipov_2017/alpha_e_mp4_SF6#
{
"id": "alpha_e_mp4_SF6",
"material": "SF6",
"file": "SF6/sharipov_2017__alpha_e_mp4_SF6.csv",
"table": "tbl_5c6a04a7a846",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "check"
}
Table A1 alpha_e(MP4) = 4.665 A^3 (31.48 au): static electronic, clamped nuclei; without ZPV (0.023) and the large pure vibrational PV (1.893 A^3 = 12.77 au). No uncertainty stated.
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.