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 `__ · :doc:`Catalogue ` · :doc:`Review register ` DOI: `10\.1088/1361\-6455/aa7f80 `__ **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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 :doc:`review register ` for the checks and decisions.