Search Results (5)

Understanding the interface between soluble metal complexes and supported metal particles is important in order to reveal reaction mechanisms in a new generation of highly active homogeneous transition metal catalysts. In this study, we show that, in the case of palladium forming on a carbon (Pd/C) catalyst from a soluble Pd(0) complex Pd₂dba₃, the nature of deposited particles on a carbon surface turns out to be much richer than previously assumed, even if a very simple experimental procedure is utilized without the use of additional reagents and procedures. In the process of obtaining a heterogeneous Pd/C catalyst, highly active “hidden” metal centers are formed on the carbon surface, which are leached out by the solvent and demonstrate diverse reactivity in the solution phase. The results indicate that heterogeneous catalysts may naturally contain trace amounts of molecular monometallic centers of a different nature by easily transforming them to the homogeneous catalytic system. In line with a modern concept, a heterogenized homogeneous catalyst precursor was found to leach first, leaving metal nanoparticles mostly intact on the surface. In this study, we point out that the previously neglected soft leaching process contributes to high catalyst activity. The results we obtained demand for leaching to be reconsidered as a flexible tool for catalyst construction and for the rational design of highly active and selective homogeneous catalytic systems, starting from easily available heterogeneous catalyst precursors. Full article

The charged forms of π–conjugated chromophores are relevant in the field of organic electronics as charge carriers in optoelectronic devices, but also as energy storage substrates in organic batteries. In this context, intramolecular reorganization energy plays an important role in controlling material efficiency. In this work, we investigate how the diradical character influences the reorganization energies of holes and electrons by considering a library of diradicaloid chromophores. We determine the reorganization energies with the four-point adiabatic potential method using quantum–chemical calculations at density functional theory (DFT) level. To assess the role of diradical character, we compare the results obtained, assuming both closed-shell and open-shell representations of the neutral species. The study shows how the diradical character impacts the geometrical and electronic structure of neutral species, which in turn control the magnitude of reorganization energies for both charge carriers. Based on computed geometries of neutral and charged species, we propose a simple scheme to rationalize the small, computed reorganization energies for both n-type and p-type charge transport. The study is supplemented with the calculation of intermolecular electronic couplings governing charge transport for selected diradicals, further supporting the ambipolar character of the investigated diradicals. Full article

The aim of this study is to develop a regularization method for boundary value problems for a parabolic equation. A singularly perturbed boundary value problem on the semiaxis is considered in the case of a “simple” rational turning point. To prove the asymptotic convergence of the series, the maximum principle is used. Full article

The aim of the research is to develop the regularization method. By Lomov’s regularization method, we constructed a uniform asymptotic solution of the singularly perturbed Cauchy problem for a parabolic equation in the case of violation of stability conditions of the limit-operator spectrum. The problem with a “simple” turning point is considered in the case, when the eigenvalue vanishes at $t=0$ and has the form $t^{m/n}a\left(t\right)$. The asymptotic convergence of the regularized series is proved. Full article

By Lomov’s S.A. regularization method, we constructed an asymptotic solution of the singularly perturbed Cauchy problem in a two-dimensional case in the case of violation of stability conditions of the limit-operator spectrum. In particular, the problem with a ”simple” turning point was considered, i.e., one eigenvalue vanishes for $t=0$ and has the form $t^{m/n}a\left(t\right)$ (limit operator is discretely irreversible). The regularization method allows us to construct an asymptotic solution that is uniform over the entire segment $[0,T]$ , and under additional conditions on the parameters of the singularly perturbed problem and its right-hand side, the exact solution. Full article