Vibrational spectra of the tetramethylpnikogenonium ions

The tetramethylpnikogenonium ions (CH₃)₄X⁺ (X = N, P, As, Sb) have been studied by infrared and Raman spectroscopy. Additionally, their structures and vibrational frequencies were ab initio calculated at the HF/6-31+G* and for (CH₃)₄Sb⁺ at the HF/6-31+G*/LANL2DZ level of theory. For the tetrahedral cations an assignment of the vibrational frequencies is discussed on the basis of a comparison of calculated and measured frequencies.     

Diffusion of 111Cd probes in Ga7Pt3 studied via nuclear quadrupole relaxation

Diffusion of ¹¹¹In/Cd impurity atoms was studied in Ga₇Pt₃ at the atomic level using the method of perturbed angular correlation of gamma rays (PAC). As in previous measurements on Ga₇Pd₃, probes were observed to occupy two inequivalent Ga-sublattices. Quadrupole interaction perturbation functions for each site exhibited damping at elevated temperatures that is attributed to nuclear relaxation caused by stochastic jumps of the probe atoms accompanied by reorientation of axes of the electric field gradient tensor. Fitted relaxation frequencies, proportional to mean jump frequencies of the probe, were thermally activated. Arrhenius plots revealed jump-frequency activation enthalpies of 0.94 (8) and 0.67 (4) eV for the two sites and frequency prefactors close to 1 THz. Results were similar to those found previously for Ga₇Pd₃, although jump frequencies are about 100 times lower in Ga₇Pt₃.     

Microwave absorption coefficients of atmospheric pollutants and constituents

Calculations of the transition frequencies and absorption coefficients of microwave rotational transitions are given for a number of atmospheric pollutants and constituents. New measurements of the absorption coefficients are made in the vicinity of 70 GHz. The apparatus used in these measurements is briefly described. The calculated absorption coefficients are compared with these measurements and with existing measurements at other frequencies where available. Transitions with frequencies up to about 200 GHz are considered for the molecules and radicals SO₂, O₃, H₂O, NO₂, H₂S, H₂CO, NH₃, CO, OCS, N₂O, NO, OH, O₂, SO. Also discussed are criteria for the selection of appropriate transitions for the development of high sensitivity monitors to be used in air pollution and combustion research.     

Direct magnetoelectric effect in two-layer composite structures Tb0.12Dy0.2Fe0.68-PbZr0.53Ti0.47O3 at bending and longitudinal vibrations

The direct magnetoelectric effect has been studied in samples of two-layer composites containing 8 × 6 × 0.3-mm layers of the piezoelectric material PbZr_0.53Ti_0.47O₃ and 6 × 6 × A-mm layers (A = 0.3, 0.6, 0.9, 1.2, and 1.5) of the ferromagnet Tb_0.12Dy_0.2Fe_0.68 and epoxy adhesive in the frequency range of 10–253 kHz at room temperature. It has been found that the magnetoelectric effect significantly increases at resonance frequencies (13.2–61.1 kHz) of the first harmonic of bending vibrations along the sample length, at resonance frequencies (39.5–90.7 kHz) of the first harmonic of bending vibrations along the sample width, and at resonance frequencies (123.3–141.0 kHz) of the first harmonic of longitudinal vibrations along the sample length. The magnetoelectric effect magnitudes at the resonance frequencies of the bending vibrations is found to be greater than that at the resonance frequencies of the longitudinal vibrations of the sample.     

Polyyne bending frequencies: why they vary with the square of the harmonic in the infinite limit

The vibrational frequencies of several linear polyynes HC _N H, HC _N I and IC _N I, for even-valued N up to 60, have been obtained using computational quantum chemistry. The bending normal modes have the appearance of classical transverse normal modes of a vibrating string fixed at both ends, for which the frequencies vary with the first power of the harmonic. Our calculations, however, reveal that in the limit of infinite chain length and infinite mass on the ends of the ‘molecular string’, the bending frequencies vary with the square of the harmonic, at all levels of theory. A derivation is presented to explain the discrepancy.     

Stimulated Raman spectra of a strong bichromatic field interacting with a three-level atom

We have studied the stimulated Raman spectra arising from the interaction of a three-level atom with two strong electromagnetic fields whose initially populated modes ω _a and ω _b are in resonance with the two atomic transition frequencies. The Green's function formalism has been used in the limit of high photon densities to calculate the excitation spectra near the frequencies ω = ± ω _ab = ± (ω _a - ω _b ). Expressions are derived for the relative intensities, which describe, apart from the usual Raman peak at the frequency ω = ω _ab , four pairs of lorentzian lines peaked at the frequencies ω - ω _ab = ± Ω _a /√2, ± Ω _b /√2, ± Ω and ± 2Ω, respectively, and having spectra widths of the order of 3γ₀/4. The parameter Ω is defined as Ω² = (Ω _a ² + Ω _b ²)/2, where Ω _a and Ω _b are the Rabi frequencies of the two laser fields and γ₀ is the spontaneous emission probability. Numerical calculations for selected values of the Rabi frequencies are graphically presented and discussed. Conditions have been established for which Raman gain processes are anticipated to take place.     

ac ionic conductivity of hollandite type compounds from 100 Hz to 37.0 GHz

The frequency- and temperature-dependences of a.c. ionic conductivity of one-dimensional super-ionic conductors K-priderites with a hollandite type structures were investigated from 100 Hz to 37.0 GHz. Four kinds of K-priderite, K_1.6Mg_0.8Ti_7.2O₁₆, (K_1.3, Li_0.1) Mg_0.7Ti_7.3O₁₆, K_1.6Al_1.6Ti_6.4O₁₆ and (K_1.3, Li_0.2) Al_1.5Ti_6.5O₁₆, were studied. An equivalent circuit to combine the data of the complex conductivity at low and high frequencies was proposed. The data of complex conductivity at low frequencies can be analyzed in terms of the moving box model proposed by Beyeler et al. The transport of K⁺ ions at low frequencies is characterized by the cooperative motion of the K⁺ ions with various mobilities and is accompanied with the polarization of the K⁺ ions in the channels. The ion transport across intrinsic barriers at or above microwave frequencies is characterized by the frequency-independent ionic conductivity and is interpreted by the configurational model proposed by Beyeler et al. The height of intrinsic barriers is related to the lattice constants of a crystal.     

Dielectric behaviour of cellulose acetate-based polymer electrolytes

The present work deals with the findings on the dielectric behaviour of cellulose acetate (CA) and its complexes consisting of ammonium tetrafluoroborate (NH₄BF₄) and polyethylene glycol with a molecular weight of 600?g/mol (PEG₆₀₀) that were prepared using the solution casting method. The highest ?? obtained for CA-NH₄BF₄ film was 2.18?×?10^?7 S cm^?1 and enhanced to 1.41?×?10^?5 S cm^?1 with the addition of 30?wt.% PEG₆₀₀. The dielectric behaviours of the selected samples were analyzed using complex impedance Z*, complex admittance A*, complex permittivity ?*, and complex electric modulus M*-based frequency and temperature dependence in the range of 10?Hz?C1?MHz and 303?C363?K, respectively. The variation in dielectric permittivity (?? _r and ?? _i) as a function of frequency at different temperatures exhibits a dispersive behaviour at low frequencies and decays at higher frequencies. The variation in dielectric permittivity as a function of temperature at different frequencies is typical of polar dielectrics in which the orientation of dipoles is facilitated with the rising temperature, and thereby the permittivity is increased. Modulus analysis was also performed to understand the mechanism of electrical transport process, whereas relaxation time was determined from the variation in loss tangent with temperature at different frequencies.     

The influence of heat exchange between a sensitive element and its surroundings on the specific detectivity of pyroelectric detectors

The specific detectivity of pyroelectric sensors at low frequencies is mainly influenced by the thermal conditions within the sensor. The temperature noise caused by heat exchange between the sensitive element and its surroundings is transformed into an increase of the dielectric loss due to electrothermal coupling. The complex normalized current responsivity is used to calculate the influence of thermal conditions. While the absolute value ¦T_R¦ gives the frequency response of the sensitivity, the additional dielectric loss tan δ_T is deduced from the imaginary part. The loss due to electrothermal coupling tan δ_T exceeds the dielectric intrinsic loss tan δ_i for most sensor structures within the frequency range up to 100 Hz. Thus, the maximum attainable specific detectivity of a pyroelectric sensor at normal operation frequencies is dependent on its construction rather than on the material parameter dielectric intrinsic loss tan δ_i which is frequently referred to. The effect of electrothermal coupling can be employed in sensors with reduced sensitivity at low frequencies as used for FTIR-devices.     

Ultrasonic frequencies correlated with the volume changes of the q[110] mode for the first-order phase transition in NH4CI

We correlate here by means of γ-Grüneisen relations the volume changes with the ultrasonic frequencies of the q[110] mode of NH₄Cl for the first-order phase transition in this crystal. The ultrasonic frequencies were calculated by a method, which we have developed, using the length-change data from the literature at pressures of 0, 0.2, 0.4 and 0.6 kbar in the first-order phase region of NH4Cl.

Our calculated frequencies are in very good agreement with the observed data from the literature for the q[11 0] mode at these pressures. This shows that by correlating the volume changes with the ultrasonic frequencies, the observed behaviour of NH₄Cl can be explained adequately near the first-order phase transition in this crystalline system.     

Raman spectroscopic studies on matrix-isolated arsenic and antimony molecules As4 and Sb4 in noble gas matrices

The Raman spectra of As₄ and Sb₄ molecules have been studied in neon, argon, krypton, and xenon matrices at 7 K. The vibrational frequencies of the As₄ molecule are up to 17 cm⁻¹ higher than the experimental gas phase data. This evident blue-shift is not caused by matrix effects but originates from an underestimation of the fundamentals in the gas phase as a course of the elevated temperatures. The observed frequencies of As₄ and Sb₄ show a linear dependence toward the matrix host polarizability. Extrapolated values for zero polarizability which best represent a free molecule, are considered fundamental frequencies. The general valence force fields of As₄ and Sb₄ were calculated from the extrapolated frequencies.     

Velocity of hypersounds in lithium hydride by spontaneous brillouin scattering

The elastic constants of lithium hydride have been measured, at room temperature, by means of Brillouin scattering for frequencies of about 60 GHz. The results are C₁₁=6.71, C₁₂=1.7 andC₄₄=4.60 (units 10¹⁰Nm^-2). The values of C₁₁ and C₁₂ are slightly higher than that obtained for ultrasonic frequencies. The strong departure from the Cauchy relation is corroborated.     

Infrared-microwave two-photon spectra of the ν3 bands of 12CH3F and 13CH3F

Infrared-microwave two-photon spectra have been obtained for the ν₃ bands of ¹²CH₃F and ¹³CH₃F with a two-photon spectrometer employing a CO₂ laser and a computer-coupled microwave source operating in the 8–18 GHz region. Even though the intensities of the spectra for the double parity levels in these molecules are inversely proportional to the square of the microwave frequency, transitions have been observed with microwave frequencies of up to 16 GHz. Comparison of these observed two-photon frequencies to frequencies predicted from infrared laser Stark spectroscopy, and to frequencies calculated from vibration-rotation parameters obtained by fitting these and other frequencies, shows agreement to within a few MHz. Spectroscopic parameters for the ground and ν₃ excited states of the two species are reported.     

Frequency dependent kinetics of the cw CO2 laser induced reaction of CF3Br

Kinetics of the decomposition of CF₃Br at 20 torr by a cw CO₂ laser have been studied over the range of laser frequencies 1043–1085 cm^-1. At constant translational temperature the change in the rate constant with laser frequency over the frequency range is a factor of 500, comparable to the effect previously observed in CF₂ClCF₂Cl and CF₃CF₂Cl. Arrhenius plots show an activation energy of 64.9 kcal/mole, independent of frequency. The laser induced optical absorption of CF₃Br exhibits a hysteresis effect at the lower laser frequencies.     

In situ FTIR investigation of adsorption properties of sub-micron Cu2O-doped RuO2 sensing electrode of planar potentiometric pH sensor

In situ Fourier transform infrared spectroscopy (FTIR) was used to study adsorption properties of 20?mol% Cu₂O-doped RuO₂ sensing electrode (SE) screen-printed on the platinised alumina substrate of the planar electrochemical pH sensor and subsequently sintered at 800?°C. Morphology and properties of developed SEs were characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy and FTIR techniques. It was shown that both Cu₂O doping and changes in the sintering condition of the SE affected morphology and adsorption spectra of 20?mol% Cu₂O-doped RuO₂. Fundamental vibration frequencies of ruthenium?Coxygen bond at a temperature of 23?°C as well as region above fundamental frequencies for the sub-micron 20?mol% Cu₂O-doped RuO₂-SE were identified.     

Accurate rest frequencies of submillimeter-wave lines of H2D and D2H

We re-examined the submillimeter-wave transition frequencies of H₂D⁺ (J = 1₁₀ − 1₁₁ at 372.4 GHz) and D₂H⁺ (J = 1₁₀ − 1₀₁ at 691.7 GHz) to resolve suggested slight difference in velocity (v_LSR) of these species detected in the cold pre-stellar core 16293E recently. Both H₂D⁺ and D₂H⁺ were generated in a magnetically confined extended-negative glow discharge of a gaseous mixture of H₂/D₂/Ar. A combination of small improvements in various aspects of the measurements such as double modulation technique combined with a conventional frequency modulation and magnetic field modulation and more efficient signal accumulation method allowed us to improve signal-to-noise ratio, and thus to determine the transition frequencies more accurately. Both transition frequencies for the H₂D⁺ and D₂H⁺ lines have been thus determined to be 372421.385(10) and 691660.483(20) MHz, respectively. These precise rest frequencies suggest that the v_LSR of H₂D⁺ and D₂H⁺ in the pre-stellar core 16293E are indeed different as indicated in a recent astronomical observation. In addition, in this investigation, another transition of H₂D⁺ which falls in this frequency region, J = 3₂₁ − 3₂₂ transition, has been observed at 646430.293(50) MHz. As H₂D⁺ is a lightest asymmetric-top molecule and it is difficult to predict the rotational transition frequencies by using the effective asymmetric rotor Hamiltonian, any new observation of the rotational lines will be useful to improve the molecular parameters. The molecular constants for the ground state have been obtained for H₂D⁺ and D₂H⁺ by fitting these new measured frequencies together with the combination differences.     

A quadratic configuration interaction study of N2O and N2O·−

The geometries and vibrational frequencies of both N₂O and N₂O^·– were calculated at the QCISD and QCISD(T) levels of theory using aug-cc-pVDZ and aug-cc-pVTZ basis sets. The electron affinity of N₂O was determined to be ?0.15 eV. This work corroborates an earlier G2 study and suggests that the currently accepted value for the electron affinity, 0.22eV, is in error. This study represents the best calculation to date for the geometry and vibrational frequencies of N₂O^·?     

Temperature and pressure dependence of Raman active lattice mode frequencies of cubic C8H6(Br)2, evidence of a phase transition

The temperature dependence of the Raman active frequencies of the lattice modes of dibromocubane is measured below room temperature. The frequencies are linearly dependent on the temperature decreasing with increased temperature with a marked change in slope occurring at 200?K indicative of a structural phase transition. The pressure dependence of the frequencies measured at room temperature up to 24?KBar shows no evidence of a phase change. Density functional calculations of the structure and Raman frequencies of the internal modes of an isolated molecule of C₈H₆(Br)₂ indicate the molecule is slightly distorted from a cubic carbon structure.     

Infrared-microwave two-photon spectroscopy of the ν4 and ν6 bands of D2CO

Transitions in the ν₄ and ν₆ bands of D₂CO have been recorded by means of an infrared-microwave two-photon spectometer. The two-photon frequencies have been combined with frequencies obtained by infrared laser Stark and microwave spectroscopy to obtain rotational and centrifugal distortion constants for the ground, ν₄, and ν₆ states as well as vibrational frequencies and the Coriolis coupling constant for the two excited states. Expressions are reported for the linestrengths of two-photon transitions for an asymmetric rotor for the cases of parallel and perpendicular orientation of the planes of polarization of the infrared and microwave radiation.     

Distribution of surface states based on Hill and Coleman conductance technique

Hill-Coleman’s single frequency conductance technique for the determination of surface state density has been extended upto 2 kHz. A.c. conductance (G _m) and capacitance (C _m)versus gate bias (V _G) curves were obtained at various signal frequencies. Shift of the observed peaks in theG _m versus V_G curves for different signal frequencies was utilized for the determination of surface state density at different surface potentials (φ _s). Determination of surface state density for differentφ _s values was also done by Nicollian-Goetzberger method and the results compared. Results obtained by Hill-Coleman technique compare reasonably well with those obtained by the other method.