The ν6=1 state of fluoroform, HCF3: analysis of the rotational and vibrational spectra

An analysis of the ν₆=1 state of fluoroform is performed using rotational and high resolution infrared spectra. Previously radiofrequency data [Chem. Phys. Lett. 214 (1993) 265–270] and millimeter data [J. Mol. Spectrosc. 131 (1988) 1–8] were combined with new millimeter and infrared measurements, and a set of 27 parameters has been derived. A multiple fit analysis was performed confirming the assumption that the ν₆=1 excited state is not affected by intervibrational resonances.     

The ν1 and ν3 stretching fundamental bands of PD3

The infrared (IR) spectrum of PD₃ has been recorded in the 1580–1800 cm⁻¹ range at a resolution of 0.0027 cm⁻¹. About 2400 rovibrational transitions with J^′=K^′22 have been measured and assigned to the ν₁ (A₁) and ν₃ (E) stretching fundamentals. These include 506 “perturbation-allowed” transitions with selection rules Δ(k−l)=±3. Splittings of the K^′′=3 lines have been observed. Effects of strong perturbations are evident in the spectrum. Therefore the rovibrational Hamiltonian adopted for the analysis explicitly takes into account the Coriolis and k-type interactions between the v₁=1 and v₃=1 states, and includes also several essential resonances within these states. The rotational structure in the v₁=1 and v₃=1 vibrational states up to J^′=K^′=18 was reproduced by fitting simultaneously all experimental data. Thirty-four parameters reproduced 1950 transitions retained in the final cycle with a standard deviation of the fit equal to 4.9 × 10⁻⁴ cm⁻¹ (about the precision of the experimental measurements).     

High-resolution infrared study of the 2ν3 (A1, E) and ν1 + ν3 (E) bands of NF3

The 2ν₃ overtone (A₁, E) and the ν₁ + ν₃ (E) combination bands of the oblate symmetric top ¹⁴NF₃ were studied by FTIR spectroscopy with a resolution of 2.5 × 10⁻³ cm⁻¹. Nearly 500 lines up to K_max/J_max = 30/43 were observed for the weak A₁ component reaching the v₃ = 2⁰ substate (1803.1302 cm⁻¹), the majority of which corresponded to reinforced K = 3p-type transitions. For the strong E component reaching the v₃ = 2^±2 substate (1810.4239 cm⁻¹), about 3550 transitions were assigned up to K_max/J_max = 65/69, favoring a clear observation of the ℓ(4, −2) and ℓ(4, 4) splittings within the kℓ = −2 and +4 sublevels, respectively. The two v₃ = 2 substates are linked by the ℓ(2, 2)- and ℓ(2, −1)-type interactions, providing severe crossings, respectively, at K′ = 6 and near K′ = 24 on the v₃ = 2⁺² side. A model working in the D-reduction and including all these ℓ-type interactions could reproduce together 3695 nonzero weighted experimental data (NZW) through 33 free parameters with a standard deviation of σ = 0.357 × 10⁻³  cm⁻¹. As for the ν₁ + ν₃ (E) combination band, about 3690 lines were assigned up to K_max/J_max = 45/55. Its v₁ = v₃ = 1 upper state (1931.577 5 cm⁻¹) was treated using the same model recently applied to the v₃ = 1 (E, 907.5413 cm⁻¹) state. It yielded 21 free parameters through 3282 NZW experimental data, adjusted with σ = 0.344 × 10⁻³  cm⁻¹ in the D-reduction. For the two excited states, the small and unobserved ℓ(0, 6) interaction was tested as useless. To confirm the adequacy of the vibrationally isolated models used, some other reductions of the Hamiltonian were tried. For the v₃ = 2 state, the D-, L-, and LD-reductions led to similar σ’s, while the Q one was not successful. For the v₁ = v₃ = 1 state, the D- and Q-reductions gave comparable σ’s, while the QD-reduction was not as good. The corresponding unitary equivalence relations are generally more nicely fulfilled for the v₃ = 2 state than for the v₁ = v₃ = 1 state. The three derivable anharmonicity constants in cm⁻¹ are x₃₃ = −4.1528, g₃₃ = +1.8235 and x₁₃ = −7.9652.     

Self-broadening, self-shift and self-mixing in the ν2, 2ν2 and ν4 bands of NH3

Using Fourier-transform spectra (Bruker IFS 120 HR, resolution ≈0.004 cm⁻¹) of NH₃ in nine branches of the ν₂, 2ν₂ and ν₄ bands, self-broadening and self-shift as well as self-mixing coefficients have been determined at room temperature (T=295 K) for more than 350 rovibrational lines located in the spectral range 1000–1800 cm⁻¹. A non-linear least-squares multispectrum fitting procedure, including line mixing effects, has been used to retrieve successively the line parameters from 11 experimental spectra recorded at different pressures of pure NH₃. The accuracies of self-broadening coefficients are estimated to be better than 2% for most lines. The mean accuracies of line-mixing and line-shift data are estimated to be about 15% and 25%, respectively. The results are compared with previous measurements and with values calculated using a semiclassical model based upon the Robert–Bonamy formalism that reproduces rather well the systematic experimental J and K quantum number dependencies of the self-broadening coefficients.The results concerning line mixing demonstrate a large amount of coupling between the symmetric and asymmetric components of inversion doublets mainly in the ν₄ band. The line mixing parameters are both positive and negative. More than two thirds of the lines studied here have a positive shift coefficient. However, for most of them the shift coefficients are negative in the 2ν₂ band. They are positive for the R branch of the ν₂ band and for the ^PR and ^RP branches of the ν₄ band. For the other branches they are both positive and negative. Some components of inversion doublets illustrate a correlation between line mixing and shift phenomena demonstrated by a quadratic pressure dependence of line position.     

Self-broadening coefficients in the ν2 and ν5 bands of CH3F at 183 and 298 K

The self-broadening coefficients of 33 rovibrational lines in the ν₂ and ν₅ bands of ¹²CH₃F were measured at a sample temperature of 183 K using a diode-laser spectrometer. We have also realized the measurement of these coefficients at room temperature for 10 of these lines in order to determine their temperature dependence. These results were obtained by fitting to the experimental profile the Voigt lineshape and the Rautian and Galatry models taking into account the collisional narrowing. Calculations of the self-broadening coefficients were also performed for the same temperatures from a semiclassical model involving only electrostatic interactions in the intermolecular potential. The calculated values are significantly larger than the experimental data for both temperatures but the J-dependences of the self-broadenings are well reproduced. Moreover, the theoretical temperature dependence of these coefficients is in good agreement with that derived from the measurements.     

Absorption spectrum of nitrous acid for the ν1+2ν3 band studied with continuous-wave cavity ring-down spectroscopy and theoretical calculations

We present the high resolution absorption measurements of gaseous HONO at room temperature using continuous-wave cavity ring-down spectroscopy in the near-infrared region between 6017 and 6067 cm⁻¹ at a resolution of 1 pm (0.037 cm⁻¹). For the trans-HONO isomer an extensive analysis of the ν₁+2ν₃ combination band 6045.8089 cm^–1 was performed starting from the results of a previous study for the 1¹ and 3¹ vibrational states [Guilmot J-M, Godefroid M, Herman M. Rovibrational parameters for trans-nitrous acid. J Mol Spectrosc 1993;160:387–400]. The present combination band is perturbed because of the existence of several dark states of HONO which could not be identified unambiguously. The rotational constants achieved for the 1¹3² state deviate slightly from the values which are predicted from the rotational constants achieved in the previous studies for the 1¹ and 3¹ vibrational states of trans-HONO.     

High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands

We report a rovibrational analysis of the ν₄ and ν₆ fundamentals and the 2ν₅ overtone of HNSO from high-resolution Fourier transform infrared spectra. The ν₆ band (out-of-plane bend) centred at 757.5 cm⁻¹ is c-type. The ν₄ band (HNS bend) centred at 905.9 cm⁻¹ is predominantly a-type with a very weak b-type component (). Numerous global perturbations and localized avoided crossings affecting the v₄ = 1 rotational levels were successfully treated by inclusion of Fermi and c-axis Coriolis resonance terms between v₄ = 1 and v₅ = 2, and a b-axis Coriolis resonance term between v₄ = 1 and v₆ = 1. The latter term gives rise to an avoided crossing with an extraordinary ΔK_a = 5 selection rule. The Fermi resonance between v₄ = 1 and v₅ = 2 gives rise to strong mixing of their rotational wavefunctions in the vicinity of K_a = 18. The resultant borrowing of intensity made it possible for 2ν₅ transitions in the range K_a = 16–19 to be assigned and included in a global rovibrational treatment of all three band systems.     

Measurements of line intensities and determination of transition moment parameters from experimental data for the ν1 and ν3 bands of D2S

First measurements of line intensities for ν₁ and ν₃ bands of D₂³²S are reported. About 300 intensities of D₂³²S vibration–rotation lines were obtained from experimental high-resolution spectra recorded in the 1810–2051 cm⁻¹ region with the Fourier Transform Spectrometer built in Reims. Empirical values of transition moment parameters for ν₁ and ν₃ bands of D₂³²S were determined for the first time using a least-square fit to the observed intensities. Experimental D₂³²S intensities were compared with recent global variational predictions [Vl.G. Tyuterev, L. Régalia-Jarlot, D.W. Schwenke, S.A. Tashkun, Y.G. Borkov, C. R. Phys. 5 (2004) 189–199] computed from isotopically invariant potential and dipole moment functions of the hydrogen sulphide molecule. Average discrepancy between these calculations and our observed data was 0.03 cm⁻¹ for line positions of this spectral range. The discrepancy between these calculations and our measurements for the sum of line intensities was 5.5% and 3.5% for the ν₁ and ν₃ bands, correspondingly.     

The v6 = 1 and v6 = 2 vibrational states of DCF3

The high-resolution infrared spectra of DCF₃ were reinvestigated in the ν₆ fundamental band region near 500 cm⁻¹ and around 1000 cm⁻¹ with the aim to assign and analyze the overtone level of the asymmetric CF₃ bending vibration v₆ = 2.The present paper reports on the first study of both its sublevels (A₁ and E corresponding to l = 0 and ±2, respectively) through the high-resolution analysis of the overtone band and the hot and bands.The well-known “loop method”, applied to and , yielded ground state energy differences Δ(K, J) = E₀(K, J) − E₀(K − 3,J) for the range of K = 6 to 30.In the final fitting of molecular parameters, we used the strategy of fitting all upper state data together with the ground state rotational transitions.This is equivalent to that calculating separately the and coefficients of the K-dependent part of the ground state energy terms from the combination loops.All rotational constants of the ground state up to sextic order could be refined in the calculation.This led to a very accurate determination of C₀ = 0.18924413(25) cm⁻¹, , and also .In the course of analyzing simultaneously the overtone band together with the and ν₆ bands, the original assignment of the fundamental ν₆ band [Bürger et al., J. Mol. Spectrosc. 182 (1997) 34-49] was found to be incompatible with the present one. Assignments of the (k + 1, l₆ = +1)/(k − 1,l₆ = −1) levels had to be interchanged, which changed the value of Cζ₆ = −0.14198768(26) cm⁻¹ and the sign of the combination of constants C − B − Cζ in the v₆ = 1 level to a negative value.     

High-resolution FTIR and MMW study of the v4 = 2 (A1, E) excited state of NF3 near 985 cm: the axial ground state rotational constants derived by the “loop-method”

The two substates v₄ = 2⁰ (A₁, 983.702 cm⁻¹) and v₄ = 2^±2 (E, 986.622 cm⁻¹) of the oblate symmetric top molecule, ¹⁴NF₃, have been studied by high-resolution (2.5 × 10⁻³ cm⁻¹) infrared spectroscopy of the overtones and 2ν₄ − ν₄ hot bands. Transitions of the overtone, the hot band, and the previously measured fundamental band were combined to yield 585 ground state combination differences differing in K by ±3, with K_max = 36. Using the “loop-method,” a fit (standard deviation σ = 0.320 × 10⁻³ cm⁻¹) provided a complete set of the hitherto not experimentally known axial ground state constants. In units of cm⁻¹ these have the following values: . Upper state parameters were determined using a vibrationally isolated model. Considering l (2, 2) and l (2, −1) interactions between the v₄ = 2⁰ and v₄ = 2^±2 substates and effects accounting for the l (4, −2) interactions within the kl = −2 levels, 25 upper state parameters were obtained by fitting 2747 IR data (1842 transitions, 905 deduced energies, J_max = 42, K_max = 39) with σ_IR = 0.353 × 10⁻³ cm⁻¹. Moreover, millimeter-wave spectroscopy furnished 86 transitions (J_max = 16, K_max = 13) measured on the v₄ = 2 excited state. A merged fit, refining 24 parameters using the described model gave σ_IR = 0.365 × 10⁻³ cm⁻¹ andσ_MMW = 0.855 × 10⁻⁶ cm⁻¹ (26 kHz). The anharmonicity constants (in cm⁻¹) are x₄₄ = −0.84174 (2) and g₄₄ =  + 0.73014 (1). In addition to this model, the D, Q, and L reductions of the rovibrational Hamiltonian were tested. Standard deviations σ_IR = 0.375 × 10⁻³ cm⁻¹ and σ_MMW = 0.865 × 10⁻⁶ cm⁻¹ were obtained for both D and L reductions, and σ_IR = 0.392 × 10⁻³ cm⁻¹ and σ_MMW = 0.935 × 10⁻⁶ cm⁻¹ for Q reduction. The unitary equivalence of the majority of the 18 tested relations between the derived parameters was satisfactorily fulfilled. This confirms that the v₄ = 2 excited vibrational state can be considered in reasonable approximation to be isolated.     

三明治结构Tan(B3N3H6)n+1 团簇的磁性和量子输运性质

利用密度泛函理论和非平衡格林函数方法, 本文对小尺寸团簇Ta_n(B₃N₃H₆)_n+1 (n ≤ 4)的磁性和量子输运性质进行了系统的研究. 计算结果表明, 此类体系采用三明治结构作为其基态并且具有较高的稳定性. 体系的磁矩随团簇尺寸的增大而线性增大. 当把Ta_n(B₃N₃H₆)_n+1团簇耦合到Au电极上时, 形成的Au-Ta_n(B₃N₃H₆)_n+1-Au体系在有限偏压下展示出了较强的自旋过滤能力, 因而可以被看做是一类新型的低维自旋过滤器.     

A combined ab initio, Fourier transform microwave and Fourier transform infrared spectroscopic investigation of β-propiolactone: The ν8 and ν12 bands

The pure rotational spectrum of β-propiolactone (c-C₂H₄COO) has been recorded between 7 and 21 GHz using a pulsed jet Fourier transform microwave spectrometer. The resulting ground state spectroscopic constants guided the analysis of the rotationally-resolved infrared spectra of two bands that were collected using the far infrared beamline at the Canadian Light Source synchrotron. The observed modes correspond to motions best described as ring deformation (ν₁₂) at 747.2 cm⁻¹ and CO ring stretching (ν₈) at 1095.4 cm⁻¹. A global fit of 4430 a- and b-type transitions from the microwave spectrum and the two infrared bands provided an accurate set of ground state and excited state spectroscopic parameters. To complement the experimental results, the harmonic and anharmonic vibrational frequencies of all 21 infrared active modes of β-propiolactone have been calculated using the DFT B3LYP method (6-311+G(d,p), 6-311++G(2d,3p) basis sets).     

Novel photoluminescence properties of InAlO3（ZnO）m superlattice nanowires

One-dimension InAlO 3 (ZnO) m superlattice nanowires were successfully synthesized via chemical vapor deposition.Transmission electron microscopy measurements reveal that the nanowires have a periodic layered structure along the 0001 direction.The photoluminescence properties of InAlO 3 (ZnO) m superlattice nanowires are studied for the first time.The near-band-edge emissions exhibit an obvious red shift due to the formation of the localized tail states.The two peaks centered at 3.348 eV and 3.299 eV indicate a lever phenomenon at the low-temperature region.A new luminescence mechanism is proposed,combined with the special energy band structure of InAlO 3 (ZnO) m.     

Synthesis and electrical properties of In2O3(ZnO)m superlattice nanobelt

One-dimensional（ID） In₂O₃（ZnO）_m superlattice nanobelts are synthesized by a chemical vapor deposition method.The formation of the In₂O₃（ZnO）_m superlattice is verified by the high-resolution transmission electron microscopy images.The typical zigzag boundaries could be clearly observed.An additional peak at 614 cm^-1 is found in the Raman spectrum,which may correspond to the superlattice structure.The study about the electrical transport properties reveals that the In₂O₃（ZnO）_m nanobelts exhibit peculiar nonlinear I-V characteristics even under the Ohmic contact measurement condition,which are different from the Ohmic behaviors of the In-doped ZnO nanobelts.The photoelectrical measurements show the differences in the photocurrent property between them,and their transport mechanisms are also discussed.     

High-resolution FTIR spectroscopy of the 3ν2 band of PH3

High-resolution Fourier transform spectrum of phosphine (PH₃) at room temperature has been recorded in the region of the 3ν₂ band (2730-3100 cm⁻¹) at an apodized resolution of 0.005 cm⁻¹. About 200 vibration-rotation transitions have been least squares fitted with an rms of 0.00039 cm⁻¹ after taking into account the ΔK = ±3 interaction.     

Pr0.7(Sr1-xCax)0.3MnO3多晶体系中的小极化子性质

采用基于柠檬酸体系的溶胶-凝胶法制备了Pr_0.7（Sr_1-xCa_x）_0.3MnO₃系列的多晶块材, 同时还用脉冲激光沉积技术（PLD）在SrTiO₃（100）衬底上外延生长了同一系列的薄膜, 系统研究了它们的晶格结构和电输运行为. 多晶和薄膜样品都具有正交晶格结构, 电输运行为在居里温度T_Ｃ以上的高温顺磁相都很好 关键词： 0.7（Sr_1-xCa_x）_0.3MnO₃')" href="#">Pr_0.7（Sr_1-xCa_x）_0.3MnO₃ 绝热小极化子模型 双交换作用 Jahn-Teller晶格畸变     

Magnetic properties of Nd0.9Dy0.1Fe3(BO3)4

The magnetic properties of trigonal Nd_0.9Dy_0.1Fe₃(BO₃)₄ substituted compound with the competitive Nd-Fe and Dy-Fe exchange interactions have been investigated. It has been shown that in Nd_0.9Dy_0.1Fe₃(BO₃)₄ a spontaneous spin-reorientation transition from an ease-axis state to an easy-plane occurs near 8 K. Anomalies of the magnetization curves are observed in a spin-flop transition induced by the magnetic field B‖c. The calculations were performed using a molecular-field approximation and a crystal-field model for the rare-earth subsystem. Extensive experimental data on the magnetic properties of Nd_0.9Dy_0.1Fe₃(BO₃)₄ have been interpreted and good agreement between theory and experiment has been achieved using the obtained theoretical dependences.     

Transport properties and defect analysis of La1.9Sr0.1NiO4 + δ

The oxygen flux through La_1.9Sr_0.1NiO_4 + δ has been measured as a function of oxygen activity gradient and temperature (750–1000 °C). The oxygen nonstoichiometry was determined by thermogravimetry in the temperature range of 400–1000 °C and oxygen partial pressures of 0.0002–1 atm. The total conductivity was measured over a similar range of conditions. The oxide ion partial conductivity derived from the oxygen flux data is approximately 4 orders of magnitude lower than the total, mainly p-type electronic conductivity. The defect structure was derived based on the data. Combining the oxygen flux and oxygen nonstoichiometry, the self diffusion coefficient of oxygen interstitials was evaluated.     

Microwave dielectric properties of (1 − x)(Mg0.95Co0.05)TiO3–x(Na0.5La0.5)TiO3 ceramic system

The microstructures and the microwave dielectric properties of the (1 − x)(Mg_0.95Co_0.05)TiO₃–x(Na_0.5La_0.5)TiO₃ ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg_0.95Co_0.05)Ti₂O₅ was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg_0.95Co_0.05)TiO₃–0.12(Na_0.5La_0.5)TiO₃, possessing an excellent combination of dielectric properties: ε_r  22.36, Q × f  110,000 GHz (at 9 GHz), τ_f  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.     

H3PAuPh与(H3PAu)2(1,4-C6H4)2光谱性质的密度泛函研究

用密度泛函(DFT)方法优化了配合物H₃PAuPh(a),(H₃PAu)₂(1,4-C₆H₄)₂(b)的基态的几何结构,并用含时密度泛函方法计算了它们的吸收光谱.结果表明配合物a与 b的最低能量吸收谱线的波长分别为257.5 nm和307.6 nm,皆具有C(2p)→Au(6p)电荷转移参与下的p_π 关键词： 激发态 光谱 密度泛函 3')" href="#">AuPH₃