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One useful technique for increasing the efficiency of organic dye-sensitized solar cells (DSSCs) is to extend the π-conjugated bridges between the donor (D) and the acceptor (A) units. The present study used the DFT and TD–DFT techniques to investigate the effect of lengthening the polyene bridge between the donor N, N-dimethyl-anilino and the acceptor dicyanovinyl. The results of the calculated key properties were not all in line with expectations. Planar structure was associated with increasing the π-conjugation linker, implying efficient electron transfer from the donor to the acceptor. A smaller energy gap, greater oscillator strength values, and red-shifted electronic absorption were also observed when the number of polyene units was increased. However, some results indicated that the potential of the stated dyes to operate as effective dye-sensitized solar cells is limited when the polyene bridge is extended. Increasing the polyene units causes the HOMO level to rise until it exceeds the redox potential of the electrolyte, which delays regeneration and impedes the electron transport cycle from being completed. As the number of conjugated units increases, the terminal lobes of HOMO and LUMO continue to shrink, which affects the ease of intramolecular charge transfer within the dyes. Smaller polyene chain lengths yielded the most favorable results when evaluating the efficiency of electron injection and regeneration. This means that the charge transfer mechanism between the conduction band of the semiconductor and the electrolyte is not improved by extending the polyene bridge. The open circuit voltage (VOC) was reduced from 1.23 to 0.70 V. Similarly, the excited-state duration (τ) decreased from 1.71 to 1.23 ns as the number of polyene units increased from n = 1 to n = 10. These findings are incompatible with the power conversion efficiency requirements of DSSCs. Therefore, the elongation of the polyene bridge in such D-π-A configurations rules out its application in solar cell devices. [ABSTRACT FROM AUTHOR]

Nowadays, the incorporation of nanoparticles into thermal fluids has become one of the most suitable strategies for developing high-performance fluids. An unconventional improvement of thermo–physical properties was observed with the addition of 1% wt. of nanoparticles in different types of fluids, such as molten salts, allowing for the design of more thermally efficient systems using nanofluids. Despite this, there is a lack of knowledge about the effect that nanoparticles produce on the thermal stability and the decomposition kinetics of the base fluid. The present study performs IR- and UV-vis spectroscopy along with thermogravimetric analysis (TGA) of pure nitrate and nitrate based nanofluids with the presence of SiO2 and Al2O3 nanoparticles (1% wt.). The results obtained support that nanoparticles accelerate the nitrate to nitrite decomposition at temperatures below 500 °C (up to 4%), thus confirming the catalytic role of nanoparticles in nanofluids. [ABSTRACT FROM AUTHOR]

π-Electron systems of silicon have attracted attention because of their narrow HOMO-LUMO gap and high reactivity, but the structural diversity remains limited. Herein, new dialkylboryl-substituted disilenes were synthesized by the selective desilylation-borylation of the corresponding trimethylsilyl-substituted disilenes. The dialkylboryl-substituted disilenes were fully characterized by a combination of NMR spectroscopy, MS spectrometry, single-crystal X-ray diffraction analysis, and theoretical calculations. The longest-wavelength absorption bands of boryldisilenes were bathochromically shifted compared to the corresponding silyl-substituted disilenes, indicating a substantial conjugation between π(Si=Si) and vacant 2p(B) orbitals. In the presence of 4-(dimethylamino)pyridine (DMAP), the dialkylboryl groups in the boryl-substituted disilenes were easily converted to trimethylsilyl groups, suggesting the dialkylboryl-substituted disilenes in the presence of a base serve as the surrogates of disilenyl anions (disilenides). [ABSTRACT FROM AUTHOR]

Metal dithiolene complexes—M(dmit)2—are key building blocks for magnetic, conducting, and optical molecular materials, with singular electronic structures resulting from the mixing of the metal and dmit ligand orbitals. Their use in the design of magnetic and conducting materials is linked to the control of the unpaired electrons and their localized/delocalized nature. It has been recently found that UV–Vis light can control the spin distribution of some [Cu(dmit)2]−2 salts in a direct and reversible way. In this work, we study the optical response of these salts and the origin of the differences observed in the EPR spectra under UV–Vis irradiation by means of wave function-based quantum chemistry methods. The low-lying states of the complex have been characterized and the electronic transitions with a non-negligible oscillator strength have been identified. The population of the corresponding excited states promoted by the UV–Vis absorption produces significant changes in the spin distribution, and could explain the changes observed in the system upon illumination. The interaction between neighbor [Cu(dmit)2]−2 complexes is weakly ferromagnetic, consistent with the relative orientation of the magnetic orbitals and the crystal packing, but in disagreement with previous assignments. Our results put in evidence the complex electronic structure of the [Cu(dmit)2]−2 radical and the relevance of a multideterminantal approach for an adequate analysis of their properties. [ABSTRACT FROM AUTHOR]

A method that uses the ultraviolet-visible (UV-Vis) spectrum to detect organic contamination events in water distribution systems exhibits the advantages of rapid detection, low cost, and no need for reagents. The speed, accuracy, and comprehensive analysis of such a method meet the requirements for online water quality monitoring. However, the UV-Vis spectrum is easily disturbed by environmental factors that cause fluctuations of the spectrum and result in false alarms. This study proposes an adaptive method for detecting organic contamination events in water distribution systems that uses the UV-Vis spectrum based on a semi-supervised learning model. This method modifies the baseline using dynamic orthogonal projection correction and adjusts the support vector regression model in real time. Thus, an adaptive online anomaly detection model that maximizes the use of unlabeled data is obtained. Experimental results demonstrate that the proposed method is adaptive to baseline drift and exhibits good performance in detecting organic contamination events in water distribution systems. [ABSTRACT FROM AUTHOR]