Vibration-Torsion-Rotation Study of the ν5 State of CH3CF3

An investigation of the torsion-rotation-vibration energies in the ν₅ vibrational state in CH₃CF₃ has been carried out using infrared and mm-wave spectroscopy. The lowest frequency parallel fundamental band ν₅ near 600 cm⁻¹ has been measured at a resolution of 0.00125 cm⁻¹ with Fourier transform spectroscopy for the two lowest torsional states v₆=0 and 1. The cold band (v₅=1, v₆=0)←(v₅=0, v₆=0) showed no torsional splittings and looked much like a parallel band in a C_3v molecule. The hot band (v₅=1, v₆=1)←(v₅=0, v₆=1) consisted of three distinct subbands, one for each torsional sublevel σ=0, +1, and −1. For the state (v₅=1, v₆=1), the torsional splitting was increased from ∼0.001 cm⁻¹ to ∼0.022 cm⁻¹ by torsion-mediated Fermi-type interaction primarily with the dark state (v₅=0, v₆=5). The effects of this coupling on the spectrum are striking in spite of the fact that the two interacting states are ∼100 cm⁻¹ apart and differ by four units in v₆. The large amplitude character of the state (v₅=0, v₆=5) is seen to be largely responsible for the unusual (k, σ) dependence of the energies in the state (v₅=1, v₆=1). The pure rotational spectrum in the state (v₅=1, v₆=0) has been measured between ∼50 and 370 GHz with Doppler-limited resolution; no σ-splitting was detected. The 3590 infrared and mm-wave frequencies measured here have been analyzed together with the 1494 measurements reported earlier by Wang et al. in an analysis of the vibrational ground state (2001, J. Mol. Spectrosc.205, 146-163). A good fit was obtained here by varying 36 parameters in a Hamiltonian which takes into account the interaction between the torsional stacks of levels for v₅=0 and 1, as well as the (A₁−A₂) splittings measured earlier for v₅=0. The explicit treatment of the interstack interactions is shown to lead to significant changes in the parameters (V_0,3, V_0,6) that characterize the torsional potential for v₅=0. These changes have been explained quantitatively by examining the contact transformation that is implicitly applied when the interstack coupling is neglected.     

Experimental study of the Na2 3Πg state

The 3¹Π_g state of Na₂ is experimentally investigated by using high resolution cw optical-optical double resonance spectroscopy. A single line Ar⁺ laser (total of 9 lines) is used to pump the sodium dimers from thermally populated ground state to the intermediate B¹Π_u state. Then a single mode Ti:sapphire laser is used to probe the 3¹Π_g state. Violet fluorescence from highly Rydberg excited states (mainly 2³Π_g or 3³Π_g states which are transferred from 3¹Π_g state via collisions) to the state is monitored by a filtered photomultiplier tube and a lock-in amplifier. Compared with previous studies [C.C. Tsai, J.T. Bahns, W.C. Stwalley, J. Chem. Phys. 99 (1993) 7417], a wider range of rotational quantum numbers of data field are observed. A set of Dunham coefficients and the Rydberg-Klein-Rees potential energy curve of the 3¹Π_g state are deduced from all the observed rovibrational levels.     

Observation of simultaneous ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) transitions enhanced by the resonance dipole-dipole interaction with the ν1 + ν3 and ν2 + ν3 states of the SF6 molecule

IR spectra of the solution of SF₆ molecules in liquid NF₃ at 84 K have been recorded. In a solvent transmission window of 1500–1750 cm⁻¹, two wide absorption bands with pronounced peaks in the high-frequency part are observed. The profile of these bands is explained by the influence of the resonance dipole-dipole (RDD) interaction of the states of the simultaneous transition ν₁(SF₆) + ν₃(NF₃) and ν₂(SF₆) + ν₃(NF₃) with the states (ν₁ + ν₃) and (ν₂ + ν₃) of the SF₆ molecules, respectively. The use of three isotopic modifications ³²SF₆, ³³SF₆, and ³⁴SF₆ has allowed us to vary the resonance detuning and thus to change the strength of the RDD interaction. With the liquid near the melting point being represented as a close-packed cubic crystal, the profile was calculated and its spectral characteristics were determined. The frequencies of the main peaks coincide with the experimental values accurate to the error.     

High resolution study of the 3ν1 band of SO2

The second overtone band 3ν₁ of sulfur dioxide has been studied for the first time with high resolution rotation-vibration spectroscopy. About 3000 transitions involving about 900 upper state energy levels with have been assigned to the 3ν₁ band. In the analysis, an effective Hamiltonian taking into account accidental interactions between the vibrational states (3 0 0), (2 2 0), and (0 4 1) was used. The Watson operator in A-reduction and I^r representation was used in the diagonal blocks of the Hamiltonian. As the result of analysis a set of parameters reproducing the initial experimental data with the rms = 0.00028 cm⁻¹ was obtained.     

Structural and electrical investigation of (Ag3AsS3)x(As2S3)1?x superionic glasses

Structural studies of (Ag₃AsS₃) _x (As₂S₃)_1−x chalcogenide superionic glasses in the compositional range x = 0.3–0.9 were performed by scanning electron microscopy. Temperature and compositional dependences of transmission coefficient, electrical conductivity, and activation energy were investigated     

Investigation of structural,physical and optical properties of CeO2–Bi2O3–B2O3 glasses

xCeO₂–30Bi₂O₃–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. A number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.15 to 1.61 eV, refractive index increases from 2.67 to 2.93 and density increases from 4.151 to 4.633 g/cm³. The decrease in band gap with CeO₂ doping approaches the semiconductor behavior. FTIR spectroscopy reveals that incorporation of CeO₂ into glass network helps to convert the structural units of [BO₃] into [BO₄] and results in Bi–O bond vibration of [BiO₆].     

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.     

The 2ν4 overtone bands of FClO3

The high resolution infrared spectrum of the mono-isotopic species F³⁵Cl¹⁶O₃ has been studied in the region of the 2ν₄ overtone, from 2560 to 2680 cm⁻¹. The perpendicular component is strong and clearly observed while the parallel component is very weak and almost completely hidden by the perpendicular one. Their origins differ by 12.6 cm⁻¹, the being located at higher wavenumbers. The band is perturbed by the anharmonic interaction between the v₄ = 2, l₄ = ?2 and v₂ = v₄ = v₅ = 1, l₄ = l₅ = ±1 excited states, both of E symmetry. In total 3157 transitions have been assigned, 83% of these to , 12% to , and 5% to . The three bands have been analyzed simultaneously, taking into account the Fermi resonance effective between the excited states of E symmetry. The ro-vibration parameters of the excited states have been obtained, including the deperturbed band origins of and , at 2628.5890(4) and 2619.3342(5) cm⁻¹, respectively. The W₂₄₅ anharmonic constant is equal to 4.0161(4) cm⁻¹. The x₄₄+g₄₄ and x₂₄+x₄₅+g₄₅ anharmonicity constants have been derived from the obtained band origins and those of ν₄ and ν₂ + ν₅.     

Analysis of ν2, ν4 Infrared Hot Bands of SO3: Resolution of the Puzzle of the ν1 CARS Spectrum

Further analysis of the high-resolution (0.0015 cm⁻¹) infrared spectrum of ³²S¹⁶O₃ has led to the assignment of more than 3100 hot band transitions from the ν₂ and ν₄ levels to the states 2ν₂ (l=0), ν₂+ν₄ (l=±1), and 2ν₄ (l=0,±2). These levels are strongly coupled via Fermi resonance and indirect Coriolis interactions to the ν₁ levels, which are IR-inaccessible from the ground state. The unraveling of these interactions has allowed the solution of the unusual and complicated structure of the ν₁ CARS spectrum. This has been accomplished by locating over 400 hot-band transitions to levels that contain at least 10% ν₁ character. The complex CARS spectrum results from a large number of avoided energy-level crossings between these states. Accurate rovibrational constants are deduced for all the mixed states for the first time, leading to deperturbed values of 1064.924(11), 0.000 840 93(64), and 0.000 418 19(58) cm⁻¹ for ν₁, α₁^B, and α₁^C, respectively. The uncertainties in the last digits are shown in parentheses and represent two standard deviations. In addition, new values for some of the anharmonicity constants have been obtained. Highly accurate values for the equilibrium rotational constants B_e and C_e are deduced, yielding independent, nearly identical values for the SO r_e bond length of 141.734 03(13) and 141.732 54(18) pm, respectively.     

Li2K(IO3)3与Li2NH4(IO3)3的晶体结构

本文用X射线粉末法测定了Li₂K(IO₃)₃与Li₂NH₄(IO₃)₃的晶体结构和原子参数。发现Li₃K(IO₃)₃,Li₂NH₄(IO₃)₃与Li₂Rb(IO₃)₃同晶型,属单斜晶系,空间群为P2₁/α,每个单胞含有四个化合式量。室温的点阵常数分别为α=11.198?,b=11.046?,c=8.254?,β=111.53°,及α=11.327?,b=11.078?,c=8.341?,β=111.87°。讨论了二元化合物的形成与离子半径的关系。 关键词：     

Improved multiferroic properties of La-doped 0.6BiFeO3—0.4SrTiO3 solid solution ceramics

The 0.6（Bi1-xLax）FeO 3-0.4SrTiO 3（x = 0,0.1） multiferroic ceramics are prepared by a modified Pechini method to study the effect of substitution of SrTiO3 and La in BiFeO3.The X-ray diffraction patterns confirm the single phase characteristics of all the compositions each with a rhombohedral structure.The magnetic properties of the ceramics are significantly improved by a solid solution with SrTiO3 and substitution of La.The values of the dielectric constant ε r and loss tangent tan δ of all the samples decrease with increasing frequency and become constant at room temperature.The La-doped 0.6BiFeO3-0.4SrTiO3 ceramics exhibit improved dielectric and ferroelectric properties,with higher dielectric constant enhanced remnant polarization（Pr） and lower leakage current at room temperature.Compared with a anti-ferromagnetic BiFeO3 compound,the 0.6（Bi0.9La0.1）FeO3-0.4SrTiO3 sample shows the optimal ferromagnetism with remnant magnetization M r ～ 0.135 emμ/g and ferroelectricity with Pr ～ 5.94 μC/cm 2 at room temperature.     

Influence of hydrothermally modified γ-Al2O3 on the properties of NiMo/γ-Al2O3 catalyst

The influence of hydrothermal modification of γ-Al₂O₃ on the properties of NiMo/γ-Al₂O₃ catalyst was investigated in this paper. The experimental results showed that the use of the modified γ-Al₂O₃ in the preparation of the NiMo/γ-Al₂O₃ catalyst led to the increase of the dispersion of the surface Mo and Ni oxides, favored the formation of the poly-molybdates and promoted the reduction of the active Mo oxides owing to the increase of the surface acidity of the modified γ-Al₂O₃. Therefore, the NiMo/γ-Al₂O₃ catalyst supported on the modified γ-Al₂O₃ exhibited a higher hydrodenitrogenation (HDN) activity than that supported on the untreated γ-Al₂O₃ in the temperature range of 300-340 °C.     

Synthesis and properties of Au-Fe3O4 and Ag-Fe3O4 heterodimeric nanoparticles

Monodisperse Au-Fe 3 O 4 heterodimeric nanoparticles (NPs) were prepared by injecting precursors into a hot reaction solution.The size of Au and Fe 3 O 4 particles can be controlled by changing the injection temperature.UV-Vis spectra show that the surface plasma resonance band of Au-Fe 3 O 4 heterodimeric NPs was evidently red-shifted compared with the resonance band of Au NPs of similar size.The as-prepared heterodimeric Au-Fe 3 O 4 NPs exhibited superparamagnetic properties at room temperature.The Ag-Fe 3 O 4 heterodimeric NPs were also prepared by this synthetic method simply using AgNO 3 as precursor instead of HAuCl 4.It is indicated that the reported method can be readily extended to the synthesis of other noble metal conjugated heterodimeric NPs.     

High-Resolution FTIR Spectra of CD2Cl2: Analysis of the ν3/ν7/ν9 Triad

The infrared spectra of isotopically pure CD₂³⁵Cl₂ have been recorded at a resolution of 0.0026 cm⁻¹ (FWHM) in the range 600-1160 cm⁻¹ with a Bruker IFS 120 HR Fourier transform interferometer. The absorption between 670 and 750 cm⁻¹ is due to three fundamentals, ν₃ (weak), ν₇ (very weak), and ν₉ (strong). A satisfactory analysis of the observed spectra has been obtained by including a c-Coriolis coupling between ν₃ and ν₉ and a b-Coriolis term between ν₇ and ν₉. Although no transitions could be observed for the very weak ν₇ band, its band origin could be estimated from the Coriolis interaction with ν₉. From the analysis of about 4200 assigned transitions of the ν₃ and ν₉ bands, excited state constants have been determined up to sextic terms. The Coriolis parameters obtained are compared to those calculated from a harmonic force field.     

Characteristics of Ba xSr 1–xTiO 3 thin films grown by pulsed laser ablation of rotating split targets of BaTiO 3 and SrTiO 3

We have grown heterostructures of Ba_xSr_1-xTiO₃(BST)/La_0.7Sr_0.3MnO₃(LSMO) on LaAlO₃(LAO) substrates by the pulsed laser deposition method. BST films with x=0.2,0.5,0.7 and 0.8 have been prepared using a novel rotating split-target arrangement. The lattice constant of the BST films is found to vary linearly with Ba/Sr ratio. An excellent cube-on-cube epitaxial relationship of (100)_BST||(100)_LSMO||(100)_LAO has also been obtained. Scanning electron microscopy studies have revealed smooth and crack-free BST films with a uniform grain size of about 100 nm. Dielectric measurements, made with patterned Au top electrodes and conducting LSMO bottom layers, have shown a maximum permittivity of approximately 280 at 5 kHz in BST films with x=0.7. P–E loop analyses of the Ba_0.7Sr_0.3TiO₃ and Ba_0.8Sr_0.2TiO₃ films have yielded remnant polarization values of 1.66 and 1.81C/cm², respectively. PACS 81.15Fg; 68.55Jk; 77.55+f     

Detection of3T1?3T2 and3T1?3A2 transitions of Ni by conventional Fourier transform infrared FT-IR spectroscopy

A FT-IR spectroscopic study was carried out in the region 4000–400 cm^–1 for ZnSeNi and ZnSNi at room temperature. The data obtained were examined on the basis of the energy states calculations of the (3d)ⁿ configuration, based on the defect molecule approach. The present investigation reveals the transition from the ground state to the first two excited states namely³T₁–³A₂ and³T₁–³T₂ of Ni⁺² (d⁸).     

Luminescence studies of Nd- and Yb-doped α-Y(IO3)3 and β-Y(IO3)3, transparent host matrix in the mid- and beginning of the far-infrared

α-Y(IO₃)₃ and β-Y(IO₃)₃ are transparent until 12.8 and 13.4 μm, respectively; thus they are interesting as a potential laser matrix in the mid- and beginning of the far-infrared. So, in order to investigate the properties of lanthanides- doped anhydrous yttrium iodate, polycrystalline samples of α-Y_1−xNd_x(IO₃)₃ (0.01?x?0.05), β-Y_1−xNd_x(IO₃)₃ (0.001?x?0.1), α-Y_1−xYb_x(IO₃)₃ (0.01?x?0.33) and β-Y_1−xYb_x(IO₃)₃ (0.01?x?0.25) were synthesized. For Nd³⁺ ions, fluorescent emissions from the ⁴F_3/2 multiplet were observed at 300 K under pulsed laser excitations at 750 nm and for Yb³⁺, fluorescent emissions from the ²F_5/2 multiplet were observed at 300 K under pulsed laser excitations at 980 nm. The decays of all these emissions were measured. They are exponential and the fluorescence lifetimes are in the range 0.093-0.193 ms for Nd³⁺ and 0.370-0.541 ms for Yb³⁺, depending on the nature of the host and the concentration of doping.     

CO2 laser-microwave double resonance and stark lamb-dip spectroscopy of the ν5 band of CDF3

The LMDR (laser-microwave double resonance) spectroscopy with an intense electric field was applied to the ν₅ (CF₃ degenerate stretch) fundamental band of CDF₃. The dipole moments and polarizability anisotropies in the ground and ν₅ vibrational states were determined as follows.

     

19.

Forbidden lines of the ν₃ band of ¹³CH₄: Ground-state constants     

Lary W. Pinkley  K. Narahari Rao  M. Dang-Nhu  G. Tarrago  G. Poussigue 《Journal of Molecular Spectroscopy》1976,63(3):402-444

The ν₃ fundamental vibration-rotation band of carbon-13 enriched methane (¹³CH₄) was recorded using a high-resolution vacuum infrared grating spectrograph. Forbidden transitions of this band are reported for the first time. Of the nearly 900 transitions identified, 560 are forbidden transitions and 347 of the forbidden transitions have 11 ≤ J ≤ 18. Pairs of forbidden and allowed transitions having the same upper-state energy levels were used to calculate 550 independent differences between ground-state term values. From these data, a least-squares analysis was used to calculate the following values for ground-state structure constants and their standard deviations (in cm^?1):

$\text{β}{}^{\mathrm{O}}\text{hc}\text{= 5.240820 ± 0.000056}$

,

$\text{λ}{}^{\mathrm{O}}\text{hc}\text{=?(1.0856 ± 0.0015) × 10}{}^{\mathrm{?4}}$

,

$\text{?}{}^{\mathrm{O}}\text{hc}\text{= ?(1.4174 ± 0.0034) × 10}{}^{\mathrm{?4}}$

,

$\text{η}\text{hc}\text{= ?(1.73 ± 0.37) × 10}{}^{\mathrm{?11}}$

. The 550 values for the ground-state combination differences retained for analysis can be reproduced with an overall standard deviation of 0.0155 using the stated values for the structure constants. The note added in proof refines the above constants by including the newly observed microwave data.     

20.

The ν₁ and 3ν₁ bands of HNCO     

M. Carlotti  G. di Lonardo  G. Galloni  A. Trombetti 《Journal of Molecular Spectroscopy》1976,62(2):192-200

The infrared absorption of HNCO has been measured in the region of the NH stretching fundamental and in that of the second overtone. The results for the excited states are (in cm^?1):

	Ground	$\text{ν}{}_5$
μ (D)	1.653 511 (29)	1.658 514 (23)
α (Å3)	?0.77 (32)	?0.58 (48)

     

Band	$\text{ν}{}_0$	$\text{A-}\text{B}$	B	C
$\text{ν}{}_1$	3533.1	27.0	—	—
$\text{3ν}{}_1$	10145.79	22.6713	0.368426	0.361722

Forbidden lines of the ν3 band of 13CH4: Ground-state constants

The ν₃ fundamental vibration-rotation band of carbon-13 enriched methane (¹³CH₄) was recorded using a high-resolution vacuum infrared grating spectrograph. Forbidden transitions of this band are reported for the first time. Of the nearly 900 transitions identified, 560 are forbidden transitions and 347 of the forbidden transitions have 11 ≤ J ≤ 18. Pairs of forbidden and allowed transitions having the same upper-state energy levels were used to calculate 550 independent differences between ground-state term values. From these data, a least-squares analysis was used to calculate the following values for ground-state structure constants and their standard deviations (in cm^?1):

$\text{β}{}^{\mathrm{O}}\text{hc}\text{= 5.240820 ± 0.000056}$

,

$\text{λ}{}^{\mathrm{O}}\text{hc}\text{=?(1.0856 ± 0.0015) × 10}{}^{\mathrm{?4}}$

,

$\text{?}{}^{\mathrm{O}}\text{hc}\text{= ?(1.4174 ± 0.0034) × 10}{}^{\mathrm{?4}}$

,

$\text{η}\text{hc}\text{= ?(1.73 ± 0.37) × 10}{}^{\mathrm{?11}}$

. The 550 values for the ground-state combination differences retained for analysis can be reproduced with an overall standard deviation of 0.0155 using the stated values for the structure constants. The note added in proof refines the above constants by including the newly observed microwave data.     

The ν1 and 3ν1 bands of HNCO

The infrared absorption of HNCO has been measured in the region of the NH stretching fundamental and in that of the second overtone. The results for the excited states are (in cm^?1):