A comparative multi-reference configuration interaction study of the low-lying states of two thione isomers of thiophenol

Multi-reference configuration interaction, MR-CI (including extensivity corrections, named +Q), calculations were performed on the S₀–S₃ states of cyclohexa-2,4-diene-1-thione (thione 24 ) and cyclohexa-2,5-diene-1-thione (thione 25 ), which are thione isomers of thiophenol. Several types of uncontracted MR-CIS and MR-CISD wavefunctions were employed, comprising MR-CI expansions as large as ~365 × 10⁶ configuration state functions. The nature of the studied excited states was characterized. Vertical excitation energies (ΔE) and oscillator strengths (f) were computed. The most intense transitions (S₀ → S₂ for 24 and S₀ → S₃ for 25 ) did not change with the wavefunction, although a variation as large as ~1 eV was obtained for the S₃ state of 24 , at the highest (MR-CI+Q) level. On the other hand, ΔE changed at most by ~0.56 eV for 25 as the wavefunction changes, at the same level. The S₁ state of both thiones was found to have nπ* character and is in the visible region. For 24 , S₂ and S₃ are ππ* and nπ* states, respectively, while for 25 the reverse order is obtained. S₂ and S₃ are in the range ~3.5 to 5.2 eV, again at the highest level. It is the first time that the excited states of the title molecules are studied. The computed results agree with the experimental onset of photoreactions of thiones 24 and 25 found by Reva et al (Phys. Chem. Chem. Phys., 2015 , 17, 4888).     

Pump−probe experiments at the TEMPO beamline using the low‐α operation mode of Synchrotron SOLEIL

The SOLEIL synchrotron radiation source is regularly operated in special filling modes dedicated to pump–probe experiments. Among others, the low‐α mode operation is characterized by shorter pulse duration and represents the natural bridge between 50 ps synchrotron pulses and femtosecond experiments. Here, the capabilities in low‐α mode of the experimental set‐ups developed at the TEMPO beamline to perform pump–probe experiments with soft X‐rays based on photoelectron or photon detection are presented. A 282 kHz repetition‐rate femtosecond laser is synchronized with the synchrotron radiation time structure to induce fast electronic and/or magnetic excitations. Detection is performed using a two‐dimensional space resolution plus time resolution detector based on microchannel plates equipped with a delay line. Results of time‐resolved photoelectron spectroscopy, circular dichroism and magnetic scattering experiments are reported, and their respective advantages and limitations in the framework of high‐time‐resolution pump–probe experiments compared and discussed.     

Electrospun tin-carbon nanocomposite as anode material for all solid state lithium-ion batteries

Journal of Solid State Electrochemistry - All-solid-state batteries represent the next generation of electrochemical energy storage systems. A tin-carbon nanocomposite material is prepared by the...     

Biological Applications of Macrocyclic Schiff Base Ligands and Their Metal Complexes: A Survey of the Literature (2005–2019)

This article aims to provide a survey of biological applications of Schiff base macrocycles and their metal complexes, with emphasis given to the synthesis of the compounds and to their uses as antibacterial and antifungal agents. The literature on the subject, published during the 2005–2019 period, is shortly reviewed. This is an informed report collecting information on the addressed topic in a concise systematic way, and can be expected to be useful as a fast literature catalogue for researchers working on this and related domains.     

Analysis by DSC of the drying and sintering processes of alkoxide-derived SiO2–ZrO2 gels

The drying and sintering processes of SiO₂–ZrO₂ alkoxide-derived gels have been studied by means of DSC technique. In the drying process, most part of water and alcohols are removed from the gels. For the SiO₂ gel such elimination occurs at the end of the drying process, however for the ZrO₂ gel this elimination occurs during the whole drying time. An intermediate behavior is observed for the binary system SiO₂–ZrO₂ gels. In the sintering process, the DSC technique allows to determine the elimination of water and alcohols retained within the structure (open or close pores) and the well-known hydroxyl condensation of silica gel between 700° and 800°C is also observed. The ZrO₂ gel shows the final hydroxyl condensation at the heating temperature of 600°C. For the binary SiO₂–ZrO₂ gels, the hydroxyl condensation has been associated to the activation energy needed for the dissociation of silica hydroxyls. This energy decreases with the ZrO₂ concentration in the gel resulting in a sintering treatment of 500°C leading to the entire hydroxyl condensation for the gel with 75% ZrO₂–25% SiO₂.

By studying the temperature of the DSC peaks, it is possible to know the temperature at which most part of water and alcohols are leaving the gel, and these results can be used in order to select the corresponding drying or sintering schedules for obtaining a well-fabricated material.     

Unusual photochemical C-N bond cleavage in the novel methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate

The structure, preferred conformers, vibrational spectrum, and photochemical behavior of the novel azirine, methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate (MCMAC) were investigated in low-temperature matrixes and in the neat solid amorphous state by infrared spectroscopy and quantum-chemical calculations. Two conformers of the compound were observed in argon, krypton, and xenon matrixes, in agreement with the DFT(B3LYP)/6-311++G(d,p) and MP2/6-311++G(d,p) theoretical calculations. Both conformers were found to exhibit the carboxylic ester group in the cis conformation, differing in the arrangement defined by the O=C-C-Cl dihedral angle (cis and trans, for Ct and Cc forms, respectively). The Ct conformer was found to be the most stable conformer in the gaseous phase as well as in both argon and krypton matrixes, whereas the more polar Cc conformer became the most stable form in the xenon matrix and in the neat solid amorphous phase. In situ broadband UV (lambda > 235 nm) excitation of matrix-isolated MCMAC led to azirine ring C-C and C-N bond cleavages, the latter process corresponding to the most efficient reaction channel. The photochemical cleavage of the C-N bond had never been previously observed in the case of aliphatic 2H-azirines. Two electron withdrawing substituents (methoxycarbonyl group and chlorine atom) are connected to the azirine ring in the novel MCMAC azirine. The simultaneous presence of these two groups accelerates intersystem crossing toward the triplet state where cleavage of the C-N bond takes place. The primary photoproducts resulting from the C-N and C-C ring-opening reactions were also found to undergo further photochemical decarbonylation or decarboxylation reactions.     

Effect of the π Bridge and Acceptor on Intramolecular Charge Transfer in Push–Pull Cationic Chromophores: An Ultrafast Spectroscopic and TD‐DFT Computational Study

Three (donor–π–acceptor)⁺ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials.     

Solubility of metal atoms in helium droplets: exploring the effect of the well depth using the coinage metals Cu and Ag

We report a theoretical investigation of the solution properties of Cu and Ag atoms dissolved in He clusters. Employing our recent ab initio ground state pair potential for Me-He (Me = Ag, Cu), we simulated the species Me@He (n) (n = 2-100) by means of diffusion Monte Carlo (DMC) obtaining exact information on their energetics and the structural properties. In particular, we investigated the sensitivity of structural details on the well depth of the two interaction potentials. Whereas Ag structures the first He solvation layer similarly, to some extent, to a positive ion such as Na(+), Cu appears to require the onset of a second solvation shell for a similar dense structure to be formed despite an interaction well of 28.4 μhartree. An additional signature of the different solution behavior between Ag and Cu appears also in the dependence of the energy required to evaporate a single He atom on the size of the MeHe(n) clusters. The absorption spectrum for the (2)P ← (2)S excitation of the metals was also simulated employing the semi-classical Lax approximation to further characterize Me@He(n) (n = 2-100) using novel accurate interaction potentials between He and the lowest (2)P state of Ag and Cu in conjunction with the Diatomic-in-Molecules approach. The results indicated that Ag exciplexes should not form via a direct vertical excitation into an attractive region of the excited manifolds and that there is an interesting dependence of the shape of the Cu excitation bands on the local structure of the first solvation shell.