Silvahusum9943

Thus, the present results can be compared directly with the previous studies.Azobis tetrazole and triazole derivatives containing long catenated nitrogen atom chains are of great interest as promising green energetic materials. However, these compounds often exhibit poor thermal stability and high impact sensitivity. Kinetics and mechanism of the primary decomposition reactions are directly related to these issues. In the present work, with the aid of highly accurate CCSD(T)-F12 quantum chemical calculations, we obtained reliable bond dissociation energies and activation barriers of thermolysis reactions for a number of N-rich heterocycles. We studied all existing 1,1'-azobistetrazoles containing an N10 chain, their counterparts with the 5,5'-bridging pattern, and the species with hydrazo- and azoxy-bridges, which are often present energetic moieties. The N8-containing azobistriazole was considered as well. For all compounds studied, the radical decomposition channel was found to be kinetically unfavorable. All species decompose via the ring-opening reaction yielding a transient azideation. Apart from this, the highly accurate gas-phase formation enthalpies were calculated at the W1-F12 level of theory for all species studied.The spectroscopy of cis-OSSO and trans-OSSO is explored and put into the context of the Venusian atmosphere, along with other sulfur compounds potentially present there, namely, S2O, C1-S2O2, trigonal-S2O2, and S3. UV-vis spectra were calculated using the nuclear ensemble approach. The calculated OSSO spectra are shown to match well with the 320-400 nm near-UV absorption previously measured on Venus, and we discuss the challenges of assigning OSSO as the Venusian near-UV absorber. The largest source of uncertainty is getting accurate concentrations of sulfur monoxide (3SO) in the upper cloud layer of Venus (60-70 km altitude) since the 3SO self-reaction is what causes cis- and trans-OSSO to form. Additionally, we employed the matrix-isolation technique to trap OSSO formed by microwave discharging a gas mixture of argon and SO2 and then depositing the mixture onto a cold window (6-12 K). Anharmonic vibrational transition frequencies and intensities were calculated at the coupled cluster level to corroborate the matrix-isolation FTIR spectra. The computationally calculated UV-vis and experimentally recorded IR spectra presented in this work aid future attempts at detecting these sulfur compounds in the Venusian atmosphere.Dihalomethanes XCH2Y (X and Y = F, Cl, Br, and I) are a class of compounds involved in several processes leading to the release of halogen atoms, ozone consumption, and aerosol particle formation. Neutral dihalomethanes have been largely studied, but chemical physics properties and processes involving their radical ions, like the pathways of their decomposition, have not been completely investigated. In this work the photodissociation dynamics of the ClCH2I molecule has been explored in the photon energy range 9-21 eV using both VUV rare gas discharge lamps and synchrotron radiation. The experiments show that, among the different fragment ions, CH2I+ and CH2Cl+, which correspond to the Cl- and I-losses, respectively, play a dominant role. The experimental ionization energy of ClCH2I and the appearance energies of the CH2I+ and CH2Cl+ ions are in agreement with the theoretical results obtained at the MP2/CCSD(T) level of theory. Computational investigations have been also performed to study the isomerization of geminal [ClCH2I]•+ into the iso-chloroiodomethane isomers [CH2I-Cl]•+ and [CH2Cl-I]•+.The ability to direct the flow of excitons enable molecular systems to perform highly advanced functions. Intramolecular energy transfer in donor-bridge-acceptor systems can occur by different mechanisms, and the ability to control the excited state energy pathways depends on the capacity to favor one process over another. Here, we show an anticorrelation between the rates of Förster and Dexter types of energy transfer in two isomeric donor-bridge-acceptor systems. Both dyads display intramolecular Förster triplet-to-singlet and Dexter triplet-to-triplet energy transfers. However, as the bridge-acceptor connection point changes, the rate of one energy transfer process increases at the same time as the other one decreases, allowing us to control the energy flow direction. This work shows how rational design can be used to tune excited state energy pathways in molecular dyads, which is of importance for advanced functions such as multiplicity conversion in future molecular materials.J-aggregates are widely used in studies of light-matter interaction and organic optoelectronic devices. Although J-aggregate films can be fabricated on salt by epitaxial growth method, the size is limited to hundreds of nanometer. In this work, with hexagonal boron nitride (h-BN) as a substrate, highly crystalline J-aggregate ultrathin films of N,N'-ditridecylperylene 3,4,9,10-tetracarboxylic diimide (PTCDI-C13) are achieved by physical vapor transport (PVT) method. Significant bathochromically shifted absorption band and narrowed 0-0 transition are observed in the monolayer PTCDI-C13 crystal on h-BN. The exciton coherence number Ncoh of monolayer J-aggregate film extracted from the photoluminescence (PL) spectrum is up to 15 at T = 140 K, which is higher than that of the epitaxially grown layer on salt. Beyond the first molecular layer, the multilayer crystal on h-BN is dominated by H-aggregates. Entinostat datasheet Further study shows that that the first molecular layer on h-BN adopts the highly ordered face-on configuration, while the overlayers adopt the edge-on motif. As a comparison, only H-aggregate PTCDI-C13 ultrathin films are found on SiO2 substrates, but no J-aggregates. The results suggest that high-quality J-aggregates can be prepared by utilizing appropriate substrates via physical vapor transport.Density functional theory (DFT) is one of the popular methods to understand the electronic structure of molecular systems based on electronic density. On the basis of this theory, several conceptual DFT descriptors have been developed which can deal with the stability, reactivity, and several other physicochemical properties of molecules. Here, we have taken a nine-atom-functionalized deltahedral Zintl cluster of germanium (Ge) to examine the alkylation reaction mechanism. The study showed that the Zintl cluster having a methyl group as a ligand, [Ge9(CH3)3-], acts as a better nucleophile than the cyanide (-CN)-substituted cluster [Ge9(CN)3-] in terms of different thermodynamic parameters like free energy, enthalpy of activation, reaction energy, etc. A detailed reaction electronic flux analysis reveals the nature of the electronic activity throughout the reaction pathway. The reaction force, Wiberg bond indices, and dual descriptor lend additional support to the reaction mechanism. It has been found that the alkylation reaction between the Zintl ion and the alkyl halide follows a SN2-like mechanism.