A review of optically pumped far-infrared laser lines from methanol isotopes

The technique of optical pumping in polar molecules is the most efficient for Far-Infrared (FIR) laser generation, providing also a versatile and powerful tool for molecular spectroscopy in this spectral region. Methanol (CH₃OH) and its isotopic varieties are the best media for optically pumped FIR laser, with over thousand lines observed, and the most widely used for investigations and applications. In this sense, it is important organize and make available catalogues of FIR laser lines as complete as possible. Since the last critical reviews of 1984 [1] on methanol and its isotopic varieties [2,3,4], over hundred papers have been published dealing with hundreds of new FIR laser lines. In 1992 a review of FIR laser lines from CH₃OH was presented [5]. In this communication we extend this work to the other methanol isotopes, namely CH₃OD, CD₃OH, CD₃OD,¹³CH₃OH,¹³CD₃OH,¹³CD₃OD, CH₃ ¹⁸OH, CH₂DOH, CHD₂OH and CH₂DOD.Work supported by FAPESP, CNPq, FAEP-Brasil, and CNR-Italia     

IR and FIR spectroscopy of 13CD3OH around the 10P(22) and 10P(24) CO2 laser lines: New FIR laser emissions,frequency measurements and assignments

By using high resolution infrared Fourier transform data on ¹³CD₃OH and the 10P(22) and 10P(24) lines of a waveguide CO₂ laser to optically pump this methanol isotope, eight new FIR laser lines were observed. The frequencies of five laser lines were directly measured by heterodyne detection with already known laser lines. Particularly interesting are the lines pumped by the 10P(24) line, since a triade of emissions could be completely assigned.     

A novel triphenylamine-based dye sensitizer supported on titania nanoparticles and the effect of titania fabrication on its optical properties

A new synthesised triphenylamine-based dye having a branched structure with one OH-ending branch able to interact with the surface hydroxyl moieties of mesoporous TiO₂ is reported. Optical properties of the dye-titania hybrid material are presented and the higher efficiency of the dye on pure anatase TiO₂ compared to the commercial Degussa P25, which contains a rutile phase component, is confirmed. The optical and chemical properties of the dye make it a promising candidate as a metal-free dye for DSSCs or as a host for a variety of transition or main group metal ions for different applications.     

Isovalent vs. aliovalent transition metal doping of zinc oxide lithium-ion battery anodes — in-depth investigation by ex situ and operando X-ray absorption spectroscopy

The precise determination of de-/lithiation mechanisms in alternative lithium-ion battery electrode materials is crucial for their potential future success, but quite challenging — e.g., due to the occurrence of multiple crystalline and (frequently) amorphous phases. Herein, we report an in-depth ex situ/operando characterization of (carbon-coated) Fe- and Co-doped zinc oxide anodes via X-ray absorption spectroscopy to probe the oxidation state and local structural environment of the different metals upon de-/lithiation. The results provide fundamental insights into the mechanism of the conversion and alloying reaction taking place for these two active materials. In addition, this comparative investigation allows for an evaluation of the impact of isovalent (Co²⁺) and aliovalent (Fe³⁺) doping on the lithiation mechanism, having an impact on the initial lithiation kinetics, while both dopants generally enable a greatly increased re-oxidation of zinc compared to pure zinc oxide and, thus, a more reversible conversion reaction.     

Osmotic and aging effects in caviar oocytes throughout water and lipid changes assessed by 1H NMR T1 and T2 relaxation and MRI

By combining NMR relaxation spectroscopy and magnetic resonance imaging techniques, unsalted (us) and salted (s) caviar (Acipenser transmontanus) oocytes were characterized over a storage period of up to 90 days. The aging and the salting effects on the two major cell constituents, water and lipids, were separately assessed. T1 and T2 decays were interpreted by assuming a two-site exchange model. At Day 0, two water compartments that were not in fast exchange were identified by the T1 relaxation measurements on the us oocytes. In the s samples, T1 decay was monoexponential. During the time of storage, an increment of the free water amount was found for the us oocytes, ascribed to an increased metabolism. T1 and T2 of the s oocytes shortened as a consequence of the osmotic stress produced by salting. Selective images showed the presence of water endowed with different regional mobility that severely changed during the storage. Lipid T1 relaxation decays collected on us and s samples were found to be biexponential, and the T1 values lengthened during storage. In us and s oocytes, the increased lipid mobility with the storage was ascribed to lipolysis. Selective images of us samples showed lipids that were confined to the cytoplasm for up to 60 days of storage.     

Modulating the Electronic and Solid-State Structure of Organic Semiconductors by Site-Specific Substitution: The Case of Tetrafluoropentacenes

The properties as well as solid-state structures, singlet fission, and organic field-effect transistor (OFET) performance of three tetrafluoropentacenes (1,4,8,11: 10 , 1,4,9,10: 11 , 2,3,9,10: 12 ) are compared herein. The novel compounds 10 and 11 were synthesized in high purity from the corresponding 6,13-etheno-bridged precursors by reaction with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate at elevated temperatures. Although most of the molecular properties of the compounds are similar, their chemical reactivity and crystal structures differ considerably. Isomer 10 undergoes the orbital symmetry forbidden thermal [4+4] dimerization, whereas 11 and 12 are much less reactive. The isomers 11 and 12 crystallize in a herringbone motif, but 10 prefers π–π stacking. Although the energy of the first electric dipole-allowed optical transition varies only within 370 cm⁻¹ (0.05 eV) for the neutral compounds, this amounts to roughly 1600 cm⁻¹ (0.20 eV) for radical cations and 1300 cm⁻¹ (0.16 eV) for dications. Transient spectroscopy of films of 11 and 12 reveals singlet-fission time constants (91±11, 73±3 fs, respectively) that are shorter than for pentacene (112±9 fs). OFET devices constructed from 11 and 12 show close to ideal thin-film transistor (TFT) characteristics with electron mobilities of 2×10⁻³ and 6×10⁻² cm² V⁻¹ s⁻¹, respectively.     

Optical Investigation of Metallic Colloids in Ion-Irradiated Lithium Fluoride (Lif) Crystals

The measured room-temperature absorption spectra of LiF crystals implanted with 1.5 MeV He^? ions at different ion doses are presented. The application of a theoretical model allowed us to give an estimation of the band intensities associated with various kinds of electronic defects and to study their dependence on the ion dose. The model also considers the contribution due to nanometric lithium colloids, whose formation starts in the dose range at which the production of colour centres saturates.     

Basis set effects on Cu(I) coordination in Cu-ZSM-5: a computational study

DFT calculations on the coordination of Cu⁺ to the framework oxygen atoms of Al-substituted ZSM-5 were performed by using combinations of different basis sets in order to investigate the dependence of the results on the adopted computational level. With low-end basis sets, a large basis set superposition error (BSSE) favors the coordination of Cu⁺ to three to four oxygen atoms of the framework, only two of which belong to the AlO₄ tetrahedron corresponding to the investigated T-site. More extended basis sets considerably lower the BSSE and favor the coordination of Cu⁺ to only two oxygen atoms of the AlO₄ tetrahedron. Upon interaction with NO, the Cu⁺ ion is always coordinated by two oxygen atoms of the AlO₄ tetrahedron, independently of the basis set adopted and of the coordination number before NO adsorption. The shift from three- to twofold coordination caused by the Cu⁺–NO interaction requires a deformation energy that lowers the final adsorption energy. Such an effect is relevant with low-end basis sets, whereas it is substantially absent with more extended basis sets, which favor the twofold coordination of Cu⁺ even before NO adsorption. As a result, high-end basis sets increase the NO interaction energy with respect to that calculated by low-end basis sets, in agreement with experiments and suggesting a possible re-interpretation of the catalytic properties of the investigated sites. Provided suitable scale factors are employed, the N–O stretching frequencies of adsorbed nitrogen oxide calculated by sufficiently extended basis sets turned out in fair agreement with experimental findings.     

Wooden windows: Sound insulation evaluation by means of artificial neural networks

Windows are the weakest part of a façade in terms of acoustic performance: the weighted sound insulation index (R_w), measured according to ISO 140-3, is the fundamental parameter to evaluate the façade acoustic insulation.The paper aims at developing an artificial neural network (ANN) model to estimate the R_w value of wooden windows based on a limited number of windows parameters; this is a new approach because acoustic phenomena are non-linear and affected by a plurality of factors and, therefore, usually investigated through experimentation.Data set is taken from experimental campaigns carried out at the Laboratory of Acoustics, University of Perugia. A multilayer feed-forward approach was chosen and the model was implemented in MATLAB. On the basis of the results obtained by means of a preliminary training and test campaign of several ANN architectures, five main parameters were selected as network inputs: window typology, frame and shutters thickness, number of gaskets, R_w of glazing; R_w value of the window is the network output. Different ANN configurations were trained and a root mean-square error less than 3% was obtained, comparable to measurement uncertainty.This approach allows to develop a model which, with input parameters varying within appropriate ranges, can easily estimate the acoustic performance of wooden windows without experimental campaign on prototypes, saving both money and time. If the training data set is large enough, the presented approach could be very useful for design and optimization of acoustic performance of new products.