Fourier Transform Infrared spectrum of the OCD bending mode in methanol-D1

The infrared (IR) spectra corresponding to OCD bending vibration of asymmetrically deuterated methanol species CH₂DOH have been recorded with a Fourier Transform Spectrometer. The spectrum shows a typical structure of a parallel a-type band. This is expected because the bending vibration mainly executed parallel to the symmetry axis The Q-branch lines are grouped closely around 896 cm⁻¹ and the P- and R-Branches show complex structure. Nonetheless it was possible to assign a-type P- and R-branch lines up to K value of 8 and J value up to about 20 in most cases. The Q-branch lines for higher K values can be followed to about J = 15, the presence of which confirmed the assignments. The observations suggest that in the OCD bend some energy levels are highly interacted by highly excited torsional state from the ground torsional state. A full catalogue is presented along with the effective molecular parameters. An intensity anomaly was also observed in the transitions. So far it has been possible to assign only transitions between e₀ ← e₀ states. Plausible explanations of intensity anomaly are presented. Lastly, a number of optically pumped far infrared (FIR) laser lines have been assigned either to exact or tentative quantum states. These assignments should prove valuable for production of new FIR laser lines.     

High resolution infrared spectrum of the CD2 wagging band of methanol-D2 (CHD2OH) for the lowest lying torsional vibrational state (e0)

This paper reports the analysis of the high resolution (0.0019 cm⁻¹) Fourier transform infrared (FTIR) spectrum for asymmetrically deuterated methanol CHD₂OH (methanol-D₂) at a low temperature for the CD₂ wagging band for the lowest lying trans-species (e₀). In spite of the complexity and perturbation in the spectra, assignments were possible for the CD₂ wagging band for a maximum K value of 10. In total, about 500 spectral lines have been assigned. Analysis of the spectral lines has been performed in terms of state dependent molecular parameters, Q-branch origins and asymmetry splitting. Assignments have been thoroughly confirmed using combination relations (see text). The catalogue of the assigned transition wavenumbers will help identification and prediction of far infrared (FIR) optically pumped CO₂ lasers. The absorption lines close to the several 10R and 10P CO₂ laser lines have also been identified. These should help experimentalists to optimize the power of the emission FIR laser lines and to predict new lines and should prove valuable as a laboratory support for interstellar detection in “Radio Astronomy”. To our knowledge this is the first time such vibrational infrared (IR) high resolution study in CHD₂OH is being performed.     

New measurements and analysis of the far-infrared spectrum of CH2DOH in the lowest torsional vibrational state (e0)

In this work the far infrared (FIR) absorption spectrum has been measured for the asymmetrically mono deuterated Methanol (CH₂DOH) species in the wavenumber range of 15–1200 cm⁻¹ better accuracy and signal/noise ratio than known before. Assignments have been made for b-type transitions in the lowest lying torsional vibrational state trans-(e₀) for a wide range of rotational angular momentum. The assignments have been rigorously confirmed by the residual loop defect methods. The ^rR–branch wavenumbers are analyzed by the usual state dependent expansion parameters and the Q-Branch origins. These origins have been used to calculate the torsional and torsional-rotation interaction contributions. These findings are in good agreement with predicted from the Hamiltonian model described in recent publications. A large number of assignments have also been made in the millimeter wave spectrum recorded earlier and thereby evaluated the asymmetry splitting parameters for 4 different axial rotational angular momentum quantum numbers. The analysis and interpretation of the spectra are reported. New assignments for about 260 transitions are included the text and a catalog of about 1500 transitions belonging to the e₀ species is prepared (Appendix 1) and is made available through the open server in “Research Gate” and will be freely available to others.     

A general method for preparing lanthanide oxide nanoparticles via thermal decomposition of lanthanide(III) complexes with 1-hydroxy-2-naphthoic acid and hydrazine ligands

Six new lanthanide(III) complexes (i.e., [Ln(L)₂(NA)_1.5]·3H₂O, where Ln=La(III), Pr(III), Nd(III), Sm(III), Gd(III), and Ce(III) and L and NA indicate N₂H₄ and C₁₀H₆(1-O)(2-COO), respectively) with 1-hydroxy-2-naphthoic acid [C₁₀H₆(1-O)(2-COOH)] and hydrazine (N₂H₄) as co-ligands were characterized by elemental, FTIR, UV-visible, and XRD techniques. In the FT-IR spectra, the N-N stretching frequency in the range of 981–949 cm⁻¹ demonstrates evidence of the presence of coordinated N₂H₄, indicating the bidentate bridging nature of hydrazine in the complexes. These complexes show symmetric and asymmetric COO⁻ stretching from 1444 to 1441 cm⁻¹ and 1582 to 1557 cm⁻¹, respectively, indicating bidentate coordination. TG-DTA studies revealed that the compounds underwent endothermic dehydration from 98 to 110 °C. This was followed by the exothermic decomposition of oxalate intermediates to yield the respective metal oxides as the end products. From SEM images, the average size of the metal oxide particles prepared by thermal decomposition of the complexes was determined to be 39–42 nm. The powder X-ray and SEM coupled with energy dispersive X-ray (EDX) studies revealed the presence of the respective nano-sized metal oxides. The kinetic parameters of the decomposition of the complexes were calculated using the Coats-Redfern equation.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

Extended line positions,intensities, empirical lower state energies and quantum assignments of NH3 from 6300 to 7000 cm−1

Nearly 4800 features of ammonia between 6300 and 7000 cm^?1 with intensities ≥4×10^?24 cm^?1/(molecule·cm^?2) at 296 K were measured using 16 pure NH₃ spectra recorded at various temperatures (296–185 K) with the McMath–Pierce Fourier Transform Spectrometer at Kitt Peak National Observatory, AZ. The line positions and intensities were retrieved by fitting individual spectra based on a Voigt line shape profile and then averaging the values to form the experimental linelist. The integrated intensity of the region was 4.68×10^?19 cm^?1/(molecule·cm^?2) at 296 K. Empirical lower state energies were also estimated for 3567 absorption line features using line intensities retrieved from 10 spectra recorded at gas temperature between 185 and 233 K. Finally, using Ground State Combination Differences (GSCDs) and the empirical lower state energy estimates, the quantum assignments were determined for 1096 transitions in the room temperature linelist, along with empirical upper state energies for 434 levels. The assignments correspond to seven vibrational states, as confirmed from recent ab initio calculations. The resulting composite database of ¹⁴NH₃ line parameters will provide experimental constraints to ab initio calculations and support remote sensing of gaseous bodies including the atmospheres of Earth, (exo)planets, brown dwarfs, and other astrophysical environments.     

Thermal cis–trans isomerization of triazo-benzene

1,3,5-Hydroxy-triazo-benzene (H-TAB) was synthesized through a coupling-oxidation protocol. Temperature-controlled UV, IR, and ab initio calculation were carried out to investigate the cis–trans thermal isomerization of H-TAB. In temperature-controlled UV experiments, λ_max of the π–π¹ band and for the trans conformation at 335 nm and that for the cis form at 282 nm are shifted by increased temperature; band intensities of the π–π¹ transition decrease and λ_max of the π–π¹ band is shifted toward the high-energy region. The maximum peak at 2922 cm⁻¹ is shifted to 2926 cm⁻¹, and that at 2852 cm⁻¹ is shifted to 2856 cm⁻¹ at increased temperature in the temperature-controlled IR experiment. Ab initio calculation reveals that the cis conformation of H-TAB is more stable than the trans form because the cis form has less spatial repulsion. Therefore, the ground-state energy difference induced by steric repulsion of the benzene unit is the driving force of the blue shift in the thermal IR and UV spectra for the triazo-benzene.     

Sub-millimeter wave spectroscopy of CHD2OH: a-type and asymmetry induced c-type transitions in the lowest three torsional sub-levels

The sub-millimeter wave (SMMW) spectral measurements using a fast scan backward wave oscillator based spectrometer have been carried out for asymmetrically deuterated methanol CHD₂OH (Methanol-D₂). Transition frequencies have an estimated uncertainty of about ±50 kHz. Albeit the complexity in the spectra, assignments were possible for a large number of a-type (ΔK = 0) transitions. In the course of the assignment process a strong c-type (ΔK = 1) Q-branch connecting two states of different symmetry species has been identified. This Q-branch assignment is significant because it is forbidden in the normal parent species CH₃OH. It becomes allowed in the current species due to the effects of the asymmetry introduced by the off-axis deuterium in the hindering potential to the internal rotation in the molecule. The assignments are rigorously confirmed using combination relations which required the measurement of some other related lines. To our knowledge this is the first time such symmetry breaking transitions are reported in CHD₂OH and in fact this is the first time the SMMW spectrum of CHD₂OH is being reported. Detailed spectral study of this molecule in the IR and FIR regions is in progress and will be reported elsewhere. Detailed study of the identification optically pumped FIR laser line is underway.     

Oxygen diffusion and surface exchange studies on (La0.75Sr0.25)0.95Cr0.5Mn0.5O3−δ

Oxygen tracer diffusion coefficient (D^⁎) and surface exchange coefficient (k^⁎) have been measured for (La_0.75Sr_0.25)_0.95Cr_0.5Mn_0.5O_3−δ using isotopic exchange and depth profiling by secondary ion mass spectrometry technique as a function of temperature (700–1000 °C) in dry oxygen and in a water vapour-forming gas mixture. The typical values of D^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 4 × 10^− 10 cm² s^− 1 and 3 × 10^− 8 cm² s^− 1 respectively, whereas the values of k^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 5 × 10^− 8 cm s^− 1 and 4 × 10^− 8 cm s^− 1 respectively. The apparent activation energies for D^⁎ in oxidising and reducing conditions are 0.8 eV and 1.9 eV respectively.     

Oxygen nonstoichiometry and transport properties of strontium substituted lanthanum cobaltite

Oxygen nonstoichiometry, structure and transport properties of the two compositions (La_0.6Sr_0.4)_0.99CoO_3−δ (LSC40) and La_0.85Sr_0.15CoO_3−δ (LSC15) were measured. It was found that the oxygen nonstoichiometry as a function of the temperature and oxygen partial pressure could be described using the itinerant electron model. The electrical conductivity, σ, of the materials is high (σ > 500 S cm^− 1) in the measured temperature range (650–1000 °C) and oxygen partial pressure range (0.209–10^− 4 atm). At 900 °C the electrical conductivity is 1365 and 1491 S cm^− 1 in air for LSC40 and LSC15, respectively. A linear correlation between the electrical conductivity and the oxygen vacancy concentration was found for both samples. The mobility of the electron-holes was inversely proportional with the absolute temperature indicating a metallic type conductivity for LSC40. Using electrical conductivity relaxation the chemical diffusion coefficient of oxygen was determined. It was found that accurate values of the chemical diffusion coefficient could only be obtained using a sample with a porous surface coating. The porous surface coating increased the surface exchange reaction thereby unmasking the chemical diffusion coefficient. The ionic conductivity deduced from electrical conductivity relaxation was determined to be 0.45 S cm^− 1 and 0.01 S cm^− 1 at 1000 and 650 °C, respectively. The activation energy for the ionic conductivity at a constant vacancy concentration (δ = 0.125) was found to be 0.90 eV.     

Synthesis and characterization of (Pr0.75Sr0.25)1 − xCr0.5Mn0.5O3 − δ as anode for SOFCs

The complex perovskite (Pr_0.75Sr_0.25)_1 − xCr_0.5Mn_0.5O_3 − δ (PSCM) has been prepared and studied as possible anode material for high-temperature solid oxide fuel cells (SOFCs). PSCM exhibits GdFeO₃-type structure and is both physically and chemically compatible with the conventional YSZ electrolyte. The reduction of PSCM resulted in structural change from orthorhombic Pbnm to cubic Pm-3m. Selected area electron diffraction (SAED) analysis on the reduced phases indicated the presence of a √2 × √2 × 2 superlattice. The total conductivity values of ∼ 75% dense Pr_0.75Sr_0.25Cr_0.5Mn_0.5O_3 − δ at 900 °C in air and 5% H₂/Ar are 9.6 and 0.14 S cm^− 1 respectively. The conductivity of PSCM drops with decreasing Po₂ and is a p-type conductor at all studied Po₂. The average TEC of Pr_0.75Sr_0.25Cr_0.5Mn_0.5O_3 − δ is 9.3 × 10^− 6 K^− 1, in the temperature range of 100–900 °C and is close to that of YSZ electrolyte. The anode polarization resistance of PSCM in wet 5%H₂ is 1.31 Ω cm² at 910 °C and in wet CH₄ at 930 °C; the polarization resistance is 1.29 Ω cm². PSCM was unstable at 900 °C in unhumidified hydrogen. Cell performance measurements carried out using graded PSCM and La_0.8Sr_0.2MnO₃ as anode and cathode respectively yielded a maximum power density of 0.18 W cm^− 2 in wet 5%H₂/Ar at 910 °C and the corresponding current density was 0.44 A cm^− 2 at 0.4 V. The activation energy for the electrochemical cell operating in wet (3% H₂O) 5%H₂/Ar fuel is 85 kJ mol^− 1.     

Optical temperature sensor through infrared excited blue upconversion emission in Tm3 +/Yb3 + codoped Y2O3

An analysis of the intense blue upconversion emission at 476 and 488 nm in Tm^3 +/Yb^3 + codoped Y₂O₃ under excitation power density of 86.7 W/cm² available from a diode laser emitting at 976 nm, has been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive blue upconversion emission at 476 and 488 nm in this material was recorded in the temperature range from 303 to 753 K. The maximum sensitivity derived from the FIR technique of the blue upconversion emission is approximately 0.0035 K^? 1. The results imply that Tm^3 +/Yb^3 + codoped Y₂O₃ is a potential candidate for the optical temperature sensor.     

Mid- and long-wave infrared absorption cross sections for acetonitrile

Infrared absorption cross sections for acetonitrile (methyl cyanide; CH₃CN) have been determined in the 880–1700 cm^?1 spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR) and a multipass cell with a maximum optical pathlength of 19.3 m. Spectra of acetonitrile/dry synthetic air mixtures were recorded at 0.015 cm^?1 resolution (calculated as the Bruker instrument resolution of 0.9/MOPD) at a number of temperatures between 203 and 297 K and pressures appropriate for atmospheric conditions. Intensities were calibrated using three composite acetonitrile spectra recorded at the Pacific Northwest National Laboratory. These absorption cross sections will provide an accurate basis for upper tropospheric/lower stratospheric retrievals of acetonitrile in the mid-infrared spectral region from ACE satellite data.     

Spectroscopic properties of Co2+: ZnAl2O4 nanocrystals in sol–gel derived glass–ceramics

Transparent glass–ceramics containing zinc–aluminum spinel (ZnAl₂O₄) nanocrystals doped with tetrahedrally coordinated Co²⁺ ions were obtained by the sol–gel method for the first time. The gels of composition SiO₂–Al₂O₃–ZnO–CoO were prepared at room temperature and heat-treated at temperature ranging 800–950 °C. When the gel samples were heated up to 900 °C, ZnAl₂O₄ nanocrystals were precipitated. Co²⁺ ions were located in tetrahedral sites in ZnAl₂O₄ nanocrystals. X-ray diffraction analysis shows that the crystallite sizes of ZnAl₂O₄ crystal become large with the heat-treatment temperature and time, and the crystallite diameter is in the range of 10–15 nm. The dependence of the absorption and emission spectra of the samples on heat-treatment temperature were presented. The difference in the luminescence between Co²⁺ doped glass–ceramic and Co²⁺ doped bulk crystal was analysed. The crystal field parameter D_q of 423 cm⁻¹ and the Racah parameters B of 773 cm⁻¹ and C of 3478.5 cm⁻¹ were calculated for tetrahedral Co²⁺ ions.     

Improved measurements and analysis of the far-infrared spectrum of methanol-D1 (CH2DOH) arising from trans- (e0) to gauche- (e1 & o1) states

In this work the millimeter-wave (MMW) and far infrared (FIR) absorption spectrum for the asymmetrically deuterated Methanol (CH₂DOH) species measured recently at a temperature of −60 °C with better accuracy and signal/noise (S/N) ratio than known before has been assigned for transitions originating at the lowest lying trans- to gauche-states. The entire spectrum for 50–1200 cm⁻¹ has been re-recorded recently using the Synchrotron Radiation Source coupled with the Bruker Fourier Transform Infrared (FTIR) spectrometer with a resolution of about 0.001 cm⁻¹ or better. Complete spectrum has not been exploited a great deal but it helped to entangle overlapping lines in the present work. This also fills the gap remaining in the usual FTIR in the range 400–500 cm⁻¹. Hence it is expected to help the interacting partner for the Coriolis interaction encountered earlier. The assigned transitions mostly for the axial rotational angular momentum quantum number K + 1 ← K, both for R- and Q-sub bands for wide range of rotational angular momentum quantum number. The MMW spectrum has been recalibrated and assigned for a number of Q-branches. The assignments are confirmed rigorously using closed loop residual technique. The assigned ^rR and ^rQ lines have been analyzed in terms of polynomial expansion parameters. The new assignments are presented for about 750 transitions and a grand atlas of more than 1000 lines has been prepared which will be made available through the open source server at “research gate”. The present work should be useful in the area of astrophysical detection and further understanding of the energy relaxation pathways in the molecule.     

High-resolution transmission measurements of CO2 at high temperatures for industrial applications

High-resolution transmission spectra of CO₂ in the 2.7, 4.3 and 15 μm regions at temperatures up to 1773 K and at approximately atmospheric pressure (1.00±0.01 atm) are measured and compared with line-by-line calculations based on the HITEMP-1995, HITEMP-2010, CDSD-HITEMP and CDSD-4000 databases. The spectra have been recorded in a high-temperature flow gas cell and using a Fourier transform infrared (FTIR) spectrometer at a nominal resolution of 0.125 cm^?1. The volume fractions of CO₂ in the measurements were 1, 10 and 100%. The measurements have been validated by comparison with medium-resolution data obtained by Bharadwaj and Modest [6]. The deviations between the experimental spectra and the calculations at 1773 K and the vibrational energy exchange and thermal dissociation of CO₂ at high temperatures are discussed.     

Kinetic studies of electronically conducting Yb3Al5O12 garnet

Upon reduction, originally fully transparent and insulating ytterbium alumina garnet single crystals, Yb₃Al₅O₁₂, become deeply colored and electrically conducting with a conductivity of the order of 10^− 3 Ω^− 1 cm^− 1 in the temperature range of 550 °C to 1000 °C. The redox kinetics of the material is studied by means of conductivity relaxation experiments performed at oxidising and reducing conditions. Good agreement is obtained with an optical study into the redox kinetics of Yb₃Al₅O₁₂.     

Ion and electron conduction in SrFe1−xScxO3−δ

The oxygen ion and electron transport in SrFe_1−xSc_xO_3−δ  (x = 0.1–0.3) system at 700–950 °C were studied analyzing the total conductivity dependencies on the oxygen partial pressure, pO₂. The conductivity measurements were performed both under reducing conditions (10^− 19 ≤ pO₂ ≤ 10^− 8 atm) comprising the electron-hole equilibrium point, and in oxidizing atmospheres (10^− 5 ≤ pO₂ ≤ 0.5 atm) which are characterized by extensive variations of the oxygen content studied by coulometric titration technique. The incorporation of 10% Sc³⁺ cations into the iron sublattice suppresses transition of the cubic perovskite phase into vacancy-ordered brownmillerite, thus improving ion conduction at temperatures below 850 °C. When scandium content increases, the ion conductivity becomes considerably lower. The hole mobility is thermally-activated and varies in the range of 0.001 to 0.05 cm² V^− 1 s^− 1, increasing with oxygen concentration and decreasing on Sc doping.     

Transport and phase dynamics of poly(vinyl pyrrolidone) doped plastically crystalline N-methyl-N-propylpyrrolidinium tetrafluoroborate

The plastic crystal phase forming N-methyl-N-propylpyrrolidinium tetrafluoroborate organic salt (P₁₃BF₄) was combined with 2, 5 and 10 wt.% poly(vinyl pyrrolidone) (PVP). The ternary 2 wt.% PVP/2 wt.% LiBF₄/P₁₃BF₄ was also investigated. Thermal analysis, conductivity, optical thermomicroscopy, and Nuclear Magnetic Resonance (¹¹B, ¹⁹F, ¹H, ⁷Li) were used to probe the fundamental transport processes. Both the onset of phase I and the final melting temperature were reduced with increasing additions of PVP. Conductivity in phase I was 2.6 × 10^− 4 S cm^− 1 5.2 × 10^− 4 S cm^− 1 1.1 × 10^− 4 S cm^− 1 and 3.9 × 10^− 5 S cm^− 1 for 0, 2, 5 and 10 wt.%PVP/P₁₃BF₄, respectively. Doping with 2 wt.% LiBF₄ increased the conductivity by up to an order of magnitude in phase II. Further additions of 2 wt.% PVP slightly reduced the conductivity, although it remained higher than for pure P₁₃BF₄.     

Lead free KNN/P(VDF-TrFE) 0–3 pyroelectric composite films and its infrared sensor

(K_0.5Na_0.5)NbO₃ (KNN)/[P(VDF-TrFE)70:30] composite thick films with different KNN weight ratios have been fabricated and the effect of KNN mass content on the material structure and properties have been studied in this paper. Properties of the infrared sensor based KNN/[P(VDF-TrFE)70:30] composite thick film were also systematically studied. It was found that the sample containing 30 wt.% KNN show optimal properties for pyroelectric appliance and the highest pyroelectric coefficient was 63 μCm⁻² K⁻¹. Infrared sensors using 30 wt.% KNN-70 wt.%[P(VDF-TrFE)70:30] show highest detectivity (D¹ = 3.21 × 10⁸ cm Hz^1/2 W⁻¹) at 137.3 Hz, indicating it is an promising candidate in lead-free quick response infrared detectors.