Dipole properties of PH3, PF3, PF5, PCl3, SiCl4, GeCl4, and SnCl4

Experimental and theoretical photoabsorption cross sections combined with constraints provided by the Kuhn–Reiche–Thomas sum rule, the high-energy behaviour of the dipole oscillator strength density, static dipole polarisabilities, and molar refractivity data when available are used to construct dipole oscillator strength distributions for PH₃, PF₃, PF₅, PCl₃, SiCl₄, GeCl₄, and SnCl₄. The distributions are used to predict dipole sum rules S(k), mean excitation energies I(k), and van der Waals C₆ coefficients.     

Ab initio model potentials for the alkaline-earth trimers Be3, Mg3, and Ca3

Many-body model potentials for Be₃, Mg₃, and Ca₃ clusters have been constructed with parameters fitted to the corresponding ab initio many-body energy surfaces calculated at the MP4 (SDTQ) level. These ab initio model potentials are accurate over a wide range of atom-atom distances, and are suitable for molecular dynamics simulation, collision dynamics, and other physical applications.     

Indofluorides in the AMF3-InF3 systems (A=K, Rb, Cs and M=Mg, Zn) and optical properties of Cr:K0.38Mg0.38In0.62F3

Among the fluorides disclosed in the AMF₃-InF₃ systems (A=K, Rb, Cs/M=Mg, Zn), the most favorable material for optical applications in relation with the optical quality of its crystals is K_0.38Mg_0.38In_0.62F₃ (KMI), a distorted monoclinic Magnéli-bronze, which crystals are grown from the melt. Cr³⁺ introduced in this host is optically characterized by optical spectroscopy. The chromium ions in the single crystals occupy simultaneously centrosymmetric and non-centrosymmetric sites. The broad emission band (⁴T_2 g→⁴A_2 g transition) obtained in the near infrared range is characteristic of a small crystal field effect (Dq=1476 cm⁻¹). Crystal field analysis leads to a very good agreement between calculated and experimentally observed energy levels. Furthermore, dips observed in the absorption at about 15370 cm⁻¹ are related to the calculated mixing between the wave functions, connected with the ⁴T_2 g (⁴F) and ²E_g (²G) and ²T_1 g (²G) electronic levels.     

A microwave and ab initio investigation of N2-SO3, OC-SO3, and OC-SO3-Ar

Microwave spectra have been observed for N₂-SO₃, OC-SO₃, Ar-SO₃-CO, and several of their isotopic derivatives. All three complexes are symmetric tops with little or no out-of-plane distortion of the SO₃. In Ar-SO₃-CO, the Ar and CO lie on opposite sides of the sulfur, an arrangement which has not been previously observed for trimers involving SO₃. In N₂-SO₃ and OC-SO₃, the N-S and C-S bond lengths are 2.934(12) and 2.854(12), respectively. In Ar-SO₃-CO, the C-S distance is 2.849(4) Å, which is identical, within the estimated uncertainties, to that in OC-SO₃. The Ar-S distance, on the other hand, is 3.411(11) Å, which represents a small but distinct lengthening of 0.061(12) Å relative to that previously determined for Ar-SO₃. Stark effect measurements for OC-SO₃ and Ar-SO₃-CO give dipole moments of 0.8488(13) and 0.602(15) D, respectively. The latter is very nearly equal to the difference between the dipole moments of OC-SO₃ and Ar-SO₃, suggesting that the dipole moment of the trimer is simply the vector sum of the unperturbed dimer dipole moments. Counterpoise corrected optimized geometries and binding energies have been computed at the MP2/aug-cc-pVTZ level for Ar-SO₃ (1.08 kcal/mol), N₂-SO₃ (2.60 kcal/mol), OC-SO₃ (3.92 kcal/mol), and Ar-SO₃-CO (4.90 kcal/mol). The binding energy of Ar-SO₃-CO is nearly equal to the sum of the Ar-SO₃ and OC-SO₃ binding energies, indicating that the two-body interactions on opposite sides of the SO₃ plane are not strongly coupled. Taken together, the experimental and theoretical results indicate that Ar-SO₃-CO is best regarded as a composite of Ar-SO₃ and OC-SO₃ moieties.     

The vapour phase Raman spectra,Raman band contour analyses,Coriolis coupling constants,and e-species force constants for the molecules HCF3, ClCF3, BrCF3, and ICF3

The vapour phase Raman spectra of the molecules HCF₃, ClCF₃, BrCF₃, and ICF₃ have been recorded at pressures of up to 1 atmosphere over the fundamental frequency regions. The Raman band contours of the e-species fundamentals have been analysed to yield first-order Coriolis coupling constants from which, together with the fundamental frequencies, e-species force constants of the general harmonic potential function have been evaluated. One force field was found for fluoroform, but two different ones were found for the molecules ClCF₃, BrCF₃ and ICF₃.     

Synthesis and thermoelectric properties of Cd-filled CoSb3

Cd-filled CoSb₃ samples have been synthesized by the high pressure method, and the temperature-dependent thermoelectric properties of Cd_xCo₄Sb₁₂ have been investigated from 300 to 600 K. X-ray diffraction results show that near single-phase CoSb₃ could be obtained by the high pressure method in a short time (20 min). The lattice constant increases with the increase in the Cd content. The power factor is improved and the thermal conductivity is depressed drastically by filling CoSb₃ with Cd. The maximum figure of merit reaches 0.54 at 600 K for the sample of Cd_0.38Co₄Sb₁₂, which is about four times higher than that of unfilled CoSb₃.     

Far infrared optical properties of polycrystalline NaClO3, KClO3, NaBrO3 and KBrO3

The resonant frequencies, damping constants and oscillator strengths of far infrared lattice vibrations of polycrystalline NaClO₃, KClO₃, NaBrO₃ and KBrO₃ have been obtained through classical dispersion (CD) analysis of transmission data. Space group analysis has been applied for attribution assignments and to ascertain the translational and rotational character of the respective lattice bands. The damping constants were found to be unusually large indicating short lifetimes of the excited states in spite of an apparent absence of phonon-phonon coupling. The CD analysis of the spectra also provide reliable values of oscillator strength and resonant frequency.     

Laser-induced voltage (LIV) enhancement of La2/3Sr1/3MnO3 films with Ag addition

La_2/3Sr_1/3MnO₃:Ag _x (LSMO:Ag _x , x=0, 0.04, 0.08, 0.10, 0.20, 0.30) films were grown on vicinal cut LaAlO₃ (LAO) substrates by pulsed laser deposition technique (PLD). It is found that laser-induced voltage (LIV) of LSMO:Ag _x films is improved and enhanced by Ag addition. With x increasing, figure of merit (F _m ) and anisotropic Seebeck coefficient (ΔS) of LSMO:Ag _x (x=0.08) films reach the maximum values of 28.25 mV/ns and 0.38 μV/K, respectively. The results suggest that the LIV enhancement of LSMO:Ag _x films is due to the anisotropy of the Seebeck tensor, which is produced by long range cooperative Jahn–Teller distortions with Ag addition.     

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH,and radicals

Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔH_f^o, S^o and C_p(T)) of 3 corresponding hydroperoxides CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ?H_f^o values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CH_2, CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, and CH₃SCH₂CH₂OOH are ?14.0, ?33.0, ?37.2, and ?32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.     

Level crossing investigation of the 6p 2 P 3/2 and 7p 2 P 3/2 levels of Cs133, Cs135, and Cs137

The level crossing method has been used for the investigation of the hyperfine structure of the 6p²P_3/2 and 7p²P_3/2 levels of the isotopes Cs¹³³, Cs¹³⁵, and Cs¹³⁷. For the hyperfine coupling constants a and b and for the lifetimes Τ we find: a(6p Cs¹³³)=50.72(3) g_J/?1.345, b(6p Cs¹³³)=?0.38(18) g_J/?1.345 a(7p Cs¹³³)=16.610(6) g_J/?1.3349, b(7p Cs¹³³)=?0.15(3) g_J/?1.3349 a(6p Cs¹³⁵)=53.64(4) g_J/?1.345, b(6p Cs¹³⁵)=7.41(32) g_J/?1.345 a(7p Cs¹³⁵)=17.570(6) g_J/?1.3349, b(7p Cs¹³⁵)=2.35(7) g_J/?1.3349 a(6p Cs¹³⁷)=55.80(4) g_J/?1.345, b(6p Cs¹³⁷)=7.54(20) g_J/?1.345 a(7p Cs¹³⁷)=18.274(6) g_J/?1.3349, b(7p Cs¹³⁷)=2.37(4) g_J/?1.3349 (MHz), Τ(6p²P_3/2)=29.7(2) ?1.345/g_J ns, Τ(7p²P_3/2)=135(1) ?1.3349_Jns. From a comparison with double resonance results the g_J factor of the 7p²P_3/2 level was deduced: g_J(7p²P_3/2=?1.3349(10). Level crossing measurements in the 8p²P_3/2 state of Cs¹³³ give for the g_J factor and the lifetime the following results: g_J(8p²P_3/2)=?1.3353(14), Τ(8p²P_3/2)=310(15) ns. Using recently calculated relativistic correction factors and applying corrections for core polarization and the Sternheimer effect, we obtain for the quadrupole moments: Q(Cs¹³³)=?0.0030 b, Q(Cs¹³⁵)=+0.052 b, Q(Cs¹³⁷)=+0.052 b.     

The ν3 and 2ν3 bands of SO3, SO3, SO3, and SO3

This sixth of a series of publications on the high-resolution rotation-vibration spectra of sulfur trioxide reports the results of a systematic study of the ν₃ and 2ν₃ infrared bands of the four symmetric top isotopomers ³²S¹⁶O₃, ³²S¹⁸O₃, ³⁴S¹⁶O₃, and ³⁴S¹⁸O₃. An internal coupling between the l=0(A₁^′) and l=2(E^′) levels of the 2ν₃ states was observed. This small perturbation results in a level crossing between |k−l|=9 and 12, in consequence of which the band origins of the A₁^′,l=0 “ghost” states could be determined to a high degree of accuracy. Ground and upper state rotational constants as well as vibrational anharmonicity constants are reported. The constants for the center-of-mass substituted species ³²S¹⁶O₃ and ³⁴S¹⁶O₃ vary only slightly, as do the constants for the ³²S¹⁸O₃, ³⁴S¹⁸O₃ pair. The S-O bond lengths for the vibrational ground states of the species ³²S¹⁶O₃, ³⁴S¹⁶O₃, ³²S¹⁸O₃, and ³⁴S¹⁸O₃ are, respectively, 141.981 99(1), 141.979 38(6), 141.972 78(8), and 141.969 93(8) pm, where the uncertainties, given in parentheses, are two standard deviations and refer to the last digits of the associated quantity.     

Fluorescence Spectra of Eu3+ and Tb3+ Doped Na6 Ln (BO3)3 (Ln = La,Gd, Y) Phosphors

The fluorescence properties of Eu^{3 +} and Tb³⁺ doped Na₆La(BO₃)₃, Na₆Gd(BO₃)₃, Na₆Y(BO₃)₃, Na₆(Gd, Y) (BO₃)₃ powder phosphors are reported. These phosphors display fluorescent RED and GREEN colours when droped with Eu³⁺ and Tb³⁺ ions, respectively. The best fluorescence performance was consistantly observed from the Na-Gd based hosts. The photoluminescence spectra were analysed by evaluating colour coordinates, relative intensity ratios, and stimulated emission cross-sections.     

Infrared spectra of matrix isolated BH3NH3, BD3ND3, and BH3ND3

The infrared spectra of ammonia-borane, BH₃NH₃, and two of its deuterated isotropic species, BD₃ND₃ and BH₃ND₃, isolated in argon matrix at liquid hydrogen temperature have been measured. Well resolved bands for these three isotopic species have been observed for all the fundamentals. A complete frequency assignment based on C₃v molecular symmetry has been made. A set of force constants have been calculated from the data for the two isotopes BH₃NH₃ and BD₃ND₃ using a valence force field. The agreement between experiment and frequencies calculated from these force constants for the mixed isotopic species, BH₃ND₃, substantiates the present assignment.     

Chemical shifts of Cr Kα and Kβ1, 3 lines by WDXRF spectrometry

Chemical shift and full widths at half maximum (FWHM) intensity of chromium Kα and Kβ_{1, 3} lines were examined for 12 kinds of materials containing chromium (CH₃CO₂)₇Cr₃(OH)₂, CrK(SO₄)₂.12H₂O, Cr(NO3)₃.9H₂O, Cr₂O₃, CrF₂, CrF₃.4H₂O, CrCl₂, CrCl₃, CrCl₃.6H₂O, [CrCl₂(H₂O)₄]Cl.2H₂O, Cr₂(SO₄)₃.15H₂O, CrO and Cr metal by wavelength‐dispersive X‐ray fluorescence (WDXRF) spectrometry. The chemical shifts, asymmetry index and the half‐widths of both the X‐ray emission lines show interesting trends with the oxidation state of chromium. It was observed that the chemical shifts for F compounds are higher than Cl compounds. It was also found larger chemical shifts and FWHM for Kβ_{1, 3} lines than Kα ones. It should be noted that the magnitude of chemical shifts increases with increase in the number of ligand atoms. Copyright © 2009 John Wiley & Sons, Ltd.     

Ab initio study of the structural,electronic and elastic properties of AgSbTe2, AgSbSe2, Pr3AlC,Ce3AlC,Ce3AlN,La3AlC and La3AlN compounds

In this paper, we study the structural, electronic and elastic properties of the ternary AgSbTe₂, AgSbSe₂, Pr₃AlC, Ce₃AlC, Ce₃AlN, La₃AlC and La₃AlN compounds using the full-potential linearized augmented plane wave (FP-LAPW) scheme and the pseudopotential plane wave (PP-PW) scheme in the frame of generalized gradient approximation (GGA). Results are given for the lattice parameters, bulk modulus, and its pressure derivative. The calculated lattice parameters are in good agreement with experimental results. We have determined the full set of first-order elastic constants, shear modulus, Young's modulus and Poisson's ratio of these compounds. Also, we have presented the results of the band structure, densities of states, it is found that this compounds metallic behavior, and a negative gap Г→R for Pr₃AlC. The analysis charge densities show that bonding is of covalent–ionic and ionic nature for AgSbSe₂ and AgSbTe₂ compounds.     

NMR parameters in column 13 metal fluoride compounds (AlF3, GaF3, InF3 and TlF) from first principle calculations

The relationship between the experimental ¹⁹F isotropic chemical shift and the ¹⁹F isotropic shielding calculated using the gauge including projector augmented-wave (GIPAW) method with PBE functional is investigated in the case of GaF₃, InF₃, TlF and several AlF₃ polymorphs. It is shown that the linear correlation between experimental and DFT-PBE calculated values previously established on alkali, alkaline earth and rare earth of column 3 basic fluorides (Sadoc et al., Phys. Chem. Chem. Phys. 13 (2011) 18539–18550) remains valid in the case of column 13 metal fluorides, indicating that it allows predicting ¹⁹F solid state NMR spectra of a broad range of crystalline fluorides with a relatively good accuracy. For the isostructural α-AlF₃, GaF₃ and InF₃ phases, PBE-DFT geometry optimization leads to noticeably overbended M–F–M bond angles and underestimated ²⁷Al, ⁷¹Ga and ¹¹⁵In calculated quadrupolar coupling constants. For the studied compounds, whose structures are built of corner shared MF₆ octahedra, it is shown that the electric field gradient (EFG) tensor at the cationic sites is not related to distortions of the octahedral units, in contrast to what previously observed for isolated AlF₆ octahedra in fluoroaluminates.     

Electronic structure,physico-chemical,linear and non linear optical properties analysis of coronene, 6B-, 6N-, 3B3N- substituted C24H12 using RHF,B3LYP and wB97XD methods

In this work we have investigated the effects of substituting carbon atoms with B, N and BN on the electronic structure, physico-chemical, linear and non linear optical properties of Coronene (C24H12) using HF and DFT methods. We have calculated total electronic energy E₀, zero point vibrational energy ZPVE, the enthalpy H, entropy S, molar heat capacity at constant volume C_v, ionization potential IP, electron affinity EA, hardness \(\kappa\), softness \(\vartheta\), electronegativity EN, dipole moment µ, average polarizability \(< \alpha >\), anisotropy \(\Delta \alpha\), the first molecular hyperpolarizability β_mol, second order hyperpolarizability \(\gamma_{av}\), HOMO–LUMO Energy gap E_gap, work function E_F, refractive index n, susceptibility χ, dielectric constant ε and molar refractivity MR of coronene (C24H12), the 6B-, 6N- and 3B3N- substitute-doped C24H12 C18B6H12 C18N6H12 and C18B3N3H12. The E_gap values of the molecules are between 0.91 and 2.36 eV. We observed that β_mol changes slightly when C24H12 is doped with either 6B or 6N even though their β_mol values are too small. However, by doping C24H12 with both 3B and 3N, creating a strong donor–acceptor system, a very large increase in µ and β_mol was found for C18B3N3H12. This study was done using RHF, B3LYP and wB97XD methods with the cc-pVDZ basis set. The studies have shown that doping decreases some of the above properties significantly while some increases significantly compared to pure coronene, suggesting that 6B-, 6N-, and 3B3N-doped Coronene as serious candidates for electronics, optoelectronics and photonic devices.     

Elastic, electronic, and optical properties of hypothetical SnNNi3 and CuNNi3 in comparison with superconducting ZnNNi3

The elastic, electronic, and optical properties of MNNi₃ (M=Zn, Sn, and Cu) have been calculated using the plane-wave ultrasoft pseudopotential technique, which is based on the first-principle density functional theory (DFT) with generalized gradient approximation (GGA). The optimized lattice parameters, independent elastic constants (C₁₁, C₁₂, and C₄₄), bulk modulus B, compressibility K, shear modulus G, and Poisson's ratio υ, as well as the band structures, total and atom projected densities of states and finally the optical properties of MNNi₃ have been evaluated and discussed. The electronic band structures of the two hypothetical compounds show metallic behavior just like the superconducting ZnNNi₃. Using band structures, the origin of features that appear in different optical properties of all the three compounds has been discussed. The large reflectivity of the predicted compounds in the low energy region might be useful in good candidate materials for coating to avoid solar heating.     

Structural and thermochemical properties of methyl ethyl sulfide alcohols: HOCH2SCH2CH3, CH3SCH(OH)CH3, CH3SCH2CH2OH,and radicals corresponding to loss of H atom

Sulfide alkoxy radicals are important intermediates during the partial oxidation of alkyl sulfides in atmospheric chemistry and in combustion. The atmospheric reaction sequence to formation of the alkoxy radicals includes (1) initial reaction with OH to create a radical on a carbon site, (2) the carbon radical then associates with ³O₂ to form a peroxy radical, and (3) an NO radical reacts with the peroxy radical to form an alkoxy radical (RO?) plus NO₂. This study determines structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (Δ_fH°, S°, and C_p(T)) of 3 corresponding alcohols HOCH₂SCH₂CH₃, CH₃SCH(OH)CH₃, and CH₃SCH₂CH₂OH of methyl ethyl sulfides studied in order to characterize the thermochemistry of the respective alkoxy radicals. The lowest energy molecular structures were calculated using the B3LYP density functional level of theory with the 6‐311G(2d,d,p) basis set. Standard enthalpies of formation (Δ_fH°₂₉₈) for the radicals and their parent molecules were calculated using B3LYP/6‐31 + G(2d,p), CBS‐QB3, M062x/6‐311 + g(2d,p), and G3MP2B3 methods. Isodesmic reactions were used to determine ?_fH° values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31 + G(d,p) level theory. The contributions for S°₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by CBS‐QB3 calculations, with contributions from torsion frequencies replaced by internal rotor contributions. Group additivity and hydrogen bond increment values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxide molecules and their radicals.     

Structure,electrical and magnetic properties of CaAs3, SrAs3, BaAs3 and EuAs3

The crystal structures and electrical properties of CaAs₃, SrAs₃, BaAs₃ and EuAs₃ have been studied by single crystal X-ray investigations, temperature dependent resistivity measurements and optical measurements. The structures of the triclinic CaAs₃ and monoclinic SrAs₃, BaAs₃ and EuAs₃ are closely related. The two-dimensional infinite polyanionic AS₃^2? nets are derivatives of the black phosphorus structure. CaAs₃ and BaAs₃ are semiconducting, while SrAs₃ and EuAs₃ show semimetallic behavior. The paramagnetic EuAs₃ undergoes a magnetic phase transition at 10.5 K.