sharipov_2022#
A. S. Sharipov, B. I. Loukhovitski, and E. E. Loukhovitskaya, Influence of Internal Degrees of Freedom on Electric and Related Molecular Properties, SpringerBriefs in Molecular Science (Springer, Cham, 2022)
Source record · Catalogue · Review register
DOI: 10.1007/978-3-030-84632-9
Source kind: theory
Recorded technique: A monograph summarising the authors’ earlier papers: diatomics (their Ref. 8/10, Loukhovitski, Sharipov and Starik, J. Phys. B 49, 125102 (2016), not in the library): CASSCF/Sadlej pVTZ potential, dipole and finite-field polarizability curves, the potential scaled to reference dissociation energies (Eq. 2.1), rovibrational levels by Numerov, state-specific polarizabilities averaged without (UP) and with (PP) the field’s perturbation of the potential (Eqs. 3.3-3.6); polyatomics (Ref. 41 = sharipov_2017): B97-2/Sadlej pVTZ normal-mode sections as independent 1D oscillators, alpha_el by finite-field MP4(SDQ)/Sadlej//B97-2/Sadlej (Eqs. 3.9-3.18); thermal averages Delta alpha(T) = bT + cT^2 over 10-3000 K (Eqs. 4.5, 4.6).
Materials in structured entries: CH4, CO2, O3, SF6
Dataset quantities: polarizability
Contents: 4 datasets; 0 formulas.
Curation notes#
Page numbers are pdf pages (109; pdf p. 13 is book p. 1, Chapter 1). Identity checked against the title pages (pdf pp. 4-5): title, the three authors, ISBN 978-3-030-84632-9 (eBook), SpringerBriefs in Molecular Science / in Electrical and Magnetic Properties of Atoms, Molecules, and Clusters; the preface is dated June 2021, the chapter footnotes ‘(c) ... 2022’. Units: Angstrom^3 (polarizability volumes; 1 au = 0.148184711 A^3). Numbers checked in the pdf text layer; table images checked.
DECOMPOSITION (Eqs. 3.17-3.20, pp. 47-48; as sharipov_2017): alpha(omega = 0) = alpha_el + Delta alpha^ZPV + Delta alpha^PV; alpha(omega > 0.05 au) = alpha_el + Delta alpha^ZPV (‘this term [PV] may be disregarded under UV and visible radiation’); for diatomics Delta alpha^ZPV = alpha^UP(V=0, J=0) - alpha^UP(r_e), Delta alpha^PV = alpha^PP(0,0) - alpha^UP(0,0) (Eqs. 3.7, 3.8), zero for nonpolar molecules.
WHAT SUPERSEDES sharipov_2017: nothing numerically. Table 3.4 (p. 61) reprints Table A1 of the 2017 paper (Ref. 41): the curated rows alpha_el(B97-2) / alpha_el(MP4) / ZPV / PV / b^UP x 1e6 / c^UP x 1e9 are identical (CO2 2.531 / 2.611 / 0.017 / 0.312 / 12.24 / 2.66; O3 2.727 / 2.801(a, MP4 with triples) / 0.013 / 0.312 / 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). NEW here: (1) the perturbed-potential thermal coefficients b^PP x 1e6 (A^3/K) and c^PP x 1e9 (A^3/K^2), CO2 27.71 and -4.07, O3 21.17 and -2.88, CH4 140.07 and -22.39, SF6 57.94 and -6.11 (the 2017 paper left them to its supplement, not in the library); Delta alpha^PP(T) = b^PP T + c^PP T^2 is the thermal change of the static (dielectric) polarizability, Delta alpha^UP(T) that of the optical one; (2) Table 3.1 (p. 44), the diatomics of Ref. 8 (2016): Delta alpha^ZPV = H2 0.037, N2 0.021, O2 0.016, CO 0.006; Delta alpha^PV = CO 0.020 (H2, N2, O2: ‘-’, nonpolar); other works quoted there: H2 0.035 (Kolos and Wolniewicz 1967, kolos_1967), N2 0.007 (Christiansen et al. 1998, christiansen_1998) and 0.007 (Maroulis 2003), O2 0.005 (Medved’ et al. 2001) and 0.008 (Sharipov et al. 2019), CO ZPV 0.007 and PV 0.018 (Christiansen et al. 1998); (3) the fit parameters of Eqs. 3.22 and 3.24 to more digits (p. 62): p0 = 36.875, p1 = -0.734, p2 = 1.332, p3 = 85.069, p4 = -1.504, p5 = 5.312, p6 = 4.721 D, p7 = 2.161 (2017: 36.88, -0.73, 1.33, 85.07, -1.50, 5.31, 4.72, 2.16), fitted to 17 diatomics and 50 polyatomics; Eq. 3.22 reproduces the computed ZPV within a factor 2-3, Eq. 3.24 the PV only to an order of magnitude (p. 62). In atomic units: diatomic ZPV H2 0.250, N2 0.142, O2 0.108, CO 0.040; CO PV 0.135 (computed here).
Table 3.3 (p. 56, image checked; curated rows; other works as printed): CO2 ZPV 0.017 (0.004 Bulanin et al. 1988), PV 0.312 (0.26 Bishop and Cheung 1982 = bishop_1982; 0.289 Bishop and Kirtman 1991; 0.323 Hohm 2013); O3 ZPV 0.013 (0.216 Naves et al. 2011 = naves_2011), PV 0.208 (0.209 Naves et al.); CH4 ZPV 0.099 (0.123 Raynes et al. 1988; 0.123 Marti et al. 1993; 0.130 Russell and Spackman 1995; 0.124 Ruud et al. 2000; 0.133 Kongsted and Christiansen 2007), PV 0.035 (0.034 Hohm 2013; 0.041 Kongsted and Christiansen; 0.04 Pederson et al. 2005); SF6 ZPV 0.023, PV 1.893 (2.035 Hohm 2013; 2.29 Pederson et al.). O3’s PV is 0.208 in Table 3.3 and 0.312 in Table 3.4 (the CO2 row’s digits): the 2017 paper’s inconsistency (Table 2 against Table A1) is carried into the book unchanged; Table 3.3’s 0.208 agrees with Naves et al.’s 0.209 (TC-221).
WHY THE O3 ZERO-POINT CORRECTION IS BELOW NAVES ET AL.’S (p. 55, quoted): ‘We can infer that in general, the methodology applied in [41] makes it possible to predict the effect of zero-point motion on the polarizability of polyatomic molecules properly (aside from O3). The substantial underestimate of Delta alpha^ZPV magnitude with respect to the findings of Naves et al. [46] for O3 molecule (by a factor of 15) is supposedly because of its severe multireference nature [101]. In fact, the DFT methodology applied in [41] is not capable to describe adequately the electronic structure of the ground state ozone [102], whereas the results of Naves et al. [46] were grounded on the CC method, more relevant for such systems with important nondynamical correlation effects.’ (0.013 against 0.216 A^3: 0.088 against 1.46 au; kumar_2011 quotes 1.43 au from Naves et al.). The PV values agree (0.208 or 0.312 against 0.209).
THERMAL (Chap. 4): diatomics (Fig. 4.1, p. 70; UP averages, T_vib = T_rot = T): heating from 300 to 2000 K raises the mean polarizability ‘by 2%, 0.9%, and 0.4% for H2, O2, and N2’ (figure only otherwise); the measured alpha(T) at 633 nm is compared directly, the dynamic part being below 3 % and independent of V and J (p. 70). Polyatomics: alpha(T) = alpha_el^MP4 + Delta alpha^ZPV + Delta alpha^UP(T) (Eq. 4.7); the method ‘overestimates to a little degree the low-temperature values of CO2 and CH4 polarizability (by 1% and 0.3%, respectively)’ (p. 74); Hohm and Kerl’s 633 nm data were reduced to static by the TDDFT factor 0.9813 (0.9750 at 546 nm), as in 2017. H2: Delta alpha_10 = alpha(V=1) - alpha(V=0) = 0.066 A^3 computed against Dyer and Bischel’s measured 0.067 A^3 (p. 41). Delta alpha^UP(296 K) from the UP coefficients (computed here, au): CO2 0.026, O3 0.012, CH4 0.028, SF6 0.080; Delta alpha^PP(296 K): CO2 0.053, O3 0.041, CH4 0.267, SF6 0.112 au.
SECTION 6.1, REFRACTIVITY OF A DISSOCIATING AND NONEQUILIBRIUM GAS (pp. 86-92): (6.1.1) a two-level model, <alpha>(T)/alpha(T_e = 0) = [g0 + g1 exp(-T_e/T) xi(T_e/IP)] / [g0 + g1 exp(-T_e/T)] (Eq. 6.1), xi the excited/ground polarizability ratio of Chap. 5 (Eq. 5.1, gamma = 1): a state at T_e = 0.8 IP raises the mean polarizability 1.5-fold at T = 0.5 T_e. (6.1.2) Dissociation raises the gas polarizability because the atoms’ sum exceeds the molecule’s (‘minimum polarizability principle’): Delta alpha_d = sum alpha_atom - alpha_mol > 0 for most of 19 diatomics (atoms from Schwerdtfeger and Nagle, molecules from Hohm’s review; OH 1.14 and CH 1.88 A^3 from elsewhere), with a loose linear trend Delta alpha_d / alpha_mol = 3.7e-4 Delta H_d^298 (kJ/mol, Fig. 6.2; read on the figure: H2 about 0.66, N2 and CO about 0.26-0.27, O2 about 0, NO 0.1); negative for F2, Cl2, I2. (6.1.3) O2 behind a Mach-8 shock (T0 = 300 K, P0 = 0.1 bar; T1 = 4020 K, P1 = 7.5 bar), with the state-specific O2(X) polarizabilities of their Ref. 31 and literature values for O2(a, b), O(3P), O(1D), O3: n - 1 is set mainly by O2(X); O(3P) contributes about 2.5 %, the electronically excited species 1.5 %; the T_vib, T_rot dependence of the Gladstone-Dale constant changes n - 1 by up to 1.5 %; ‘the dissociation products possess a larger polarizability than the source diatomic molecules (by 0.002 A^3 per one O2(X 3Sigma_g-) molecule decay, see Sect. 6.1.2)’ (p. 92; as printed). The Gladstone-Dale constant with the orientation term, Eq. 4.3, and state populations, Eq. 4.4, are on p. 69. No numbers usable as data.
Chap. 5 (pp. 78-83) tabulates excited/ground polarizability ratios xi (Table 5.1: H2 B 1Sigma_u+ 21.91 (MCSCF); O2 a 1Delta_g 0.95-0.97, b 1Sigma_g+ 0.96 (XMCQDPT2 and a laser-induced-grating measurement, Sharipov et al. 2019); CO a 3Pi 1.34 and 1.26): not extracted (excited states are outside the curated data).
EXTRACTED: alpha_el(MP4) of CO2, O3, CH4 and SF6 (Table 3.4), reproduced from sharipov_2017 (identical values).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
sharipov_2022/alpha_el_mp4_CO2#
{
"id": "alpha_el_mp4_CO2",
"material": "CO2",
"file": "CO2/sharipov_2022__alpha_el_mp4_CO2.csv",
"table": "tbl_268cb2f58193",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"sharipov_2017"
]
}
Table 3.4 alpha_el(MP4) = 2.611 A^3, static electronic at the B97-2 equilibrium geometry: sharipov_2017’s Table A1 value reprinted (their Ref. 41). Without ZPV 0.017 and PV 0.312.
sharipov_2022/alpha_el_mp4_O3#
{
"id": "alpha_el_mp4_O3",
"material": "O3",
"file": "O3/sharipov_2022__alpha_el_mp4_O3.csv",
"table": "tbl_268cb2f58193",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"sharipov_2017"
]
}
Table 3.4 alpha_el(MP4) = 2.801 A^3, mark a: MP4 with triple substitutions; sharipov_2017’s value reprinted. The authors’ DFT treatment of O3 is inadequate (p. 55).
sharipov_2022/alpha_el_mp4_CH4#
{
"id": "alpha_el_mp4_CH4",
"material": "CH4",
"file": "CH4/sharipov_2022__alpha_el_mp4_CH4.csv",
"table": "tbl_268cb2f58193",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"sharipov_2017"
]
}
Table 3.4 alpha_el(MP4) = 2.464 A^3; sharipov_2017’s value reprinted. ZPV 0.099, PV 0.035.
sharipov_2022/alpha_el_mp4_SF6#
{
"id": "alpha_el_mp4_SF6",
"material": "SF6",
"file": "SF6/sharipov_2022__alpha_el_mp4_SF6.csv",
"table": "tbl_268cb2f58193",
"quantity": "polarizability",
"unit": "angstrom3",
"abscissa_unit": "nm",
"use": "reproduced",
"reproduced_from": [
"sharipov_2017"
]
}
Table 3.4 alpha_el(MP4) = 4.665 A^3; sharipov_2017’s value reprinted. ZPV 0.023, PV 1.893.
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.