Study on F-F Transitions of Powdered Neodymium Compounds by Photoacoustic Spectroscopy

Photoacoustic (PA) spectra of powdered neodymium oxide (Nd 2O 3 (A type)), neodymium hydrated chloride (NdCl 3·6H 2O) and neodymium fluoride (NdF 3) were reported. PA band shifts as compared to their positions in aqueous Nd 3+ are used to calculate the nephelauxetic parameters of the compounds. The variation of these parameters and correlation with the nature of metal ligand bonding were discussed. A novel method is introduced to determine the relative values of oscillator strengths and Judd Ofelt parameters of powdered samples using PA spectroscopy. It is found that a linear correlation exists between relative values of τ 2 and oscillator strengths of hypersensitive transitions of the title compounds. It is hopetul that the new method of PA technique may serve for the Judd Ofelt quantitative analysis of powdered rare earth compounds.

A quartz-enhanced photoacoustic spectroscopy sensor for measurement of water vapor concentration in the air

A compact and highly linear quartz-enhanced photoacoustic spectroscopy（QEPAS） sensor for the measurement of water vapor concentration in the air is demonstrated. A cost-effective quartz tuning fork（QTF） is used as the sharp transducer to convert light energy into an electrical signal based on the piezoelectric effect, thereby removing the need for a photodetector. The short optical path featured by the proposed sensing system leads to a decreased size. Furthermore, a pair of microresonators is applied in the absorbance detection module（ADM） for QTF signal enhancement. Compared with the system without microresonators, the detected QTF signal is increased to approximately 7-fold. Using this optimized QEPAS sensor with the proper modulation frequency and depth, we measure the water vapor concentration in the air at atmospheric pressure and room temperature. The experimental result shows that the sensor has a high sensitivity of 1.058parts-per-million.

Relaxation process and phase transition of lanthanide liquid crystalline complexes by photoacoustic spectroscopy

Lanthanide-containing liquid crystals exhibiting smectic A phase close to room temperature were obtained. Photoacoustic （PA） spectroscopy was used to study the spectral properties and phase transitions of liquid crystalline metal complexes. It was found that PA intensity of the ligand had a relationship with the probability of nonradiative transitions, which increased in the order of Eu（tta）3L2〈La（tta）3L2〈 Tb（tta）3L2〈Er（tta）3L2. The relaxation processes of the complexes were studied in depth from two aspects： radiative and non-radiative processes, combining with their fluorescence spectra. Phase transitions of europium（m） and erbium（m） complexes, in the temperature range of 383-358 K, could be clearly monitored by both PA amplitude and PA phase signals. As the temperature crossed the transition point, PA amplitude showed a minimum and PA phase a maximum. The results indicated that PA technique could serve as a new tool for investigating the physicochemical properties of liquid crystals containing metal ions.

Studies on Intermolecular Energy Transfer and Relaxation Processes in Solid Rare Earth Complexes by Photoacoustic Spectroscopy

The photoacoustic spectra of Eu ( benz)(3) (.) ( phen)(2) ( benz: benzoate, phen: phenanthroline) and Eu-0.(8)Ln(0.2)(benz)(3)(.)(phen)(2)(Ln(3+) : La3+ or Nd3+) were reported. The intermolecular energy transfer processes were studied from the point of the nonradiative transitions. Combined with the fluorescence spectroscopy, photoacoustic spectroscopy reflects the variation of the luminescence efficiencies of solid samples. The luminescence efficiency increases when La3+ is introduced, but it decreases greatly when Nd3+ is added, which is due to the difference of intermolecular energy transfer processes. The models of intramolecular and intermolecular energy transfer and relaxation processes were established.

Trace Ammonia Detection Based on Near-Infrared Fiber-Optic Cantilever-Enhanced Photoacoustic Spectroscopy

A trace ammonia(NH3)detection system based on the near-infrared fiber-optic cantilever-enhanced photoacoustic spectroscopy(CEPAS)is proposed.A fiber-optic extrinsic Fabry-Perot interferometer(EFPI)based cantilever microphone has been designed to detect the photoacoustic pressure signal.The microphone has many advantages,such as small size and high sensitivity.A near-infrared tunable erbium-doped fiber laser(EDFL)amplified by an erbium-doped fiber amplifier(EDFA)is used as a photoacoustic excitation light source.To improve the sensitivity,the photoacoustic signal is enhanced by a photoacoustic cell with a resonant frequency of 1624 Hz.When the wavelength modulation spectroscopy(WMS)technique is applied,the weak photoacoustic signal is detected by the second-harmonic detection technique.Trace NH3 measurement experiments demonstrate that the designed fiber-optic CEPAS system has a linear response to concentrations in the range of 0 ppm‒20 ppm at the wavelength of 1522.448 nm.Moreover,the detection limit is estimated to be 3.2 ppb for a lock-in integration time of 30 s.

Photoacoustic and Fluorescence Spectroscopy of Metallomesogens Containing Lanthanide Ions

Metallomesogens Ln（bta）3L2 （Ln^3＋： La^3＋, Eu^3＋, and Ho^3＋; bta： benzoyltrifluoroacetonate; L： Schiff base） were prepared. Photoacoustic （PA） spectroscopy was used to study physicochemical properties of the liquid crystalline metal complexes. In the region of ligand absorption, PA intensity increases for Eu（bta）3L2, La（bta）3L2, and Ho（bta）3L2, in that order. It is found that the PA intensity of the ligand bears a relation to the intramolecular energy transfer process. For the first time, phase transitions of Eu（bta）3L2 from glass state to smectic A （SmA） phase and SmA phase to isotropic liquid are monitored by PA and fluorescence （FL） spectroscopy from two aspects： nonradiative and radiative transitions. The results show that PA technique may serve as a new tool for investigating the spectral properties and phase transitions of liquid crystals containing metal ions.

Diurnal variation of aethalometer correction factors and optical absorption assessment of nucleation events using multi-wavelength photoacoustic spectroscopy

A field measurement campaign was carried out during the late winter and early spring of2015 in Budapest, the capital of Hungary. The size distribution(SD) and optical absorption of carbonaceous particulate matter(CPM) was measured online using a Scanning Mobility Particle Sizer(SMPS), a 7λ-aethalometer and an inhouse developed 4λ-Photoacoustic Spectrometer. Based on the SD data, the measurement period could be classified into days with and without new particle formation events(normal days and nucleation days),although particular nucleation-like events were observed on normal days as well. Three characteristic size modes were observed with CMDs of circa 15, 25 and 110 nm that corresponded to the nucleation, traffic and heating modes. Based on the temporal behavior of these modes both types of days were divided into distinctive daily periods(heating hours,traffic hours and nucleation hours). The optical absorption spectra(OAC and AAE) also displayed the same part of day behavior to that of SD. That way this paper is among the first to assess the optical response of urban nucleation events. Due to the simultaneous measurement of OAC by the 7λ-aethalometer and a 4λ-Photoacoustic Spectrometer, OAC was measured overall at 11 wavelengths. That way aethalometer correction factors(f and C)were determined at all aethalometer wavelengths using in situ reference photoacoustic measurements. Correction factors were found to have both wavelength and time of the day variation. In the case of f, no clear trend could be observed, however, Cref values increased both as a function of wavelength.

Study on Dihydrated Praseodymium Acetylacetonate by Photoacoustic Spectra with Broad Wavelength Range

The UV Vis, NIR and MIR photoacoustic spectra of Pr(aa) 3·2H 2O were measured and most f f transition peaks of Pr 3+ are detected. The peak split and peak shift are studied also. The covalency parameter is calculated and it turns out that the covalent bonds between Pr(Ⅲ) ions and ligands exist. The results conclude that photoacoustic spectroscopy offers a unique and complementary method in analysis of solid rare earth complexes. Compared with conventional FT IR transmission and absorption approaches, PAS has the advantages of fast, nondestructive analysis and high resolution.

Photoacoustic Spectral Analysis of f-f Transitions of Neodymium Compounds with TFA and HFA

The photoacoustic(PA) spectra of neodymium oxide, Nd 2O 3(A type), and trisfluoroacetylactone(TFA) and hexafluoroacetylactone(HFA) neodymium complexes, Nd(TFA) 3·2H 2O and Nd(HFA) 3·2H 2O, are reported. The nephelauxetic ratio β , bonding parameter b 1/2 , and Sinha parameter δ were calculated based on their PA spectra. The variation of these parameters and correlation of them with the nature of metal ligand bonding were discussed. The intensity analysis of PA bands of f f transitions of neodymium ion was carried out by calculating the intensity branching vector and the environmental effects on the f f transitions of neodymium ion were discussed also. The branching vectors of f f transition of Nd(TFA) 3·2H 2O and Nd(HFA) 3·2H 2O are similar, which indicates the perturbation of the two ligand fields is similar. As the oscillator strength of the hypersensitive transition increases, the branching vector exhibits a corresponding increase. The PA spectra provide a new tool for the study of the interaction between Ln 3+ ions and the environment.

Quantitative Analysis of Lignocellulosic Components of Non-Treated and Steam Exploded Barley, Canola, Oat and Wheat Straw Using Fourier Transform Infrared Spectroscopy

Rapid and cost effective quantification of lignocellulosic components （cellulose, hemicelluloses and lignin） of agricultural biomass （barley, canola, oat and wheat） is essential to determine the effect of various pre-treatments （such as steam explosion） on biomass used as feedstock for the biofuel industry. Fourier Transformed Infrared （FTIR） spectroscopy was considered as an option to achieve this objective. Regression equations having R2 values of 0.89, 0.99 and 0.98 were developed to predict the cellulose, hemicelluloses and lignin compounds of biomass, respectively. The average absolute difference in predicted and measured cellulose, hemicellulose and lignin in agricultural biomass was 7.5%, 2.5%, and 3.8%, respectively.

Photoacoustic Studies of Colloidal Silica Particles after MeV Ion-Induced Shape Deformation

Ordered arrays of colloidal submicrometer-sized silica particles deposited onto silicon wafers were irradiated with MeV Si ions. The spherical silica particles turned into oblate particles as a result of the increase of the particle dimension perpendicular to the ion beam direction and the decrease in the parallel direction. Pulsed laser photoacoustic spectroscopy was used to study the structural changes of the silica particles after the ion-induced shape deformation. Our purpose is to correlate the mechanical vibrations generated by the pulsed laser as a function of the Si irradiation parameters: ion energy and fluence. Fast Fourier transform analysis of the photoacoustic signal was carried out in order to obtain the normal vibration modes of the system. The size, size distribution and shape of the silica particles were determined by scanning electron microscopy. Our results revealed significant structural differences between the spherical and the deformed silica particles.

Effects of pressure and noise on the stability of photoacoustic signals of trace gas components

In essence,photoacoustic spectroscopy(PAS)technology is based on the thermal effect of gas infrared absorption and the acoustic theory of photoacoustic(PA)cell.PAS technology has a good application effect on environmental monitoring in agriculture.In this study,carbon monoxide and sulfur dioxide were used as examples to explain the potential application of PAS technology and analyze the influence mechanism of pressure and noise on the PA signal.The relationship between PA signal amplitude and the concentration of gas was determined by calibration.The pressure and noise characteristics were experimentally studied,and the relationship between the PA signal and pressure&noise was obtained.The theoretical analysis and experimental results not only provided a basis for further correction of the influence of pressure,noise and other factors on PA signal but also provided technical support for improving the field application of trace gas non-resonance PA detection device for environmental monitoring in agriculture.

Study of lanthanide doped zinc oxide nanoparticles synthesized via a sonochemical method

In this work, lanthanide doped zinc oxide nanoparticles synthesized in room-temperature ionic liquid via a sonochemical method have been studied. Firstly, the cavitation bubble temperatures in 1-butyl-3-methylimidazolium hexafluorophosphate (ImPF6) have been estimated by the methyl radical recombination method. The temperatures measured in ImPF6 are in the range of 3000-4000 K. Secondly, a facile method has been proposed to prepare lanthanide (Ⅲ) doped zinc oxide nanoparticles in ImPF6 via an ultrasonic irradiation. The nanomaterials are studied by transmission electron microscopy, X-ray diffraction, photoacoustic and luminescence techniques. The results show that the relaxation processes of the samples depend strongly on the lanthanide doping. Moreover, a mechanism is proposed to interpret the formation of lanthanide (Ⅲ) doped zinc oxide nanoparticles in the ImPF6 upon ultrasonic irradiation.