A New Look at Molecular and Electronic Structure of Homoleptic Diiron(II,II) Complexes with N,N-Bidentate Ligands: Combined Experimental and Theoretical Study

Paddlewheel-type binuclear complexes featuring metal−metal bonding have been the subject of widespread interest due to fundamental concern in their electronic structures and potential applications. Here, we explore the molecular and electronic structures of diiron(II,II) complexes with N,N’-diarylformamidinate ligands. While a paddlewheel-type diiron(II,II) complex with N,N’-diphenylformamidinate ligands (DPhF) exhibits the centrosymmetric [Fe₂(μ-DPhF)₄] structure, a minor alteration in the ligand system, i. e., switching from phenyl to p-tolyl N-substituted formamidinate ligand (DTolF), resulted in the isolation of an unprecedented non-centrosymmetric [Fe(μ-DTolF)₃Fe(κ²-DTolF)] complex. Both complexes were characterized using single-crystal X-ray diffraction, magnetic measurements, ⁵⁷Fe Mössbauer spectroscopy, and cyclic voltammetry along with high-level ab-initio calculations. The results provide a new view on a range of factors controlling the ground-state electronic configuration and structural diversity of homoleptic diiron(II,II) complexes. Model calculations determined that the Mayer bond orders for Fe−Fe interactions are significantly lower than 1 and equal to 0.15 and 0.28 for [Fe₂(μ-DPhF)₄] and [Fe(μ-DTolF)₃Fe(κ²-DTolF)], respectively.     

The Role of Hydrogen Bonds and Electrostatic Interactions in Enhancing Two-Photon Absorption in Green and Yellow Fluorescent Proteins

The spectral properties of fluorescent proteins (FPs) depend on the protein environment of the chromophore (CRO). A deeper understanding of the CRO – environment interactions in terms of FPs’ spectral characteristics will allow for a rational design of novel markers with desired properties. Here, we are taking a step towards achieving this important goal. With the time-dependent density functional theory (TDDFT), we calculate one- and two-photon absorption (OPA and TPA) spectra for 5 green FPs (GFPs) and 3 yellow FPs (YFPs) differing in amino acid sequence. The goal is to reveal the roles of: (i) electrostatic interactions, (ii) hydrogen-bonds (h-bonds) and (iii) h-bonds together with distant electrostatic field in absorption spectra tuning. Our results point to design hypothesis towards FPs optimised for TPA-based applications. Both h-bonds and electrostatic interactions co-operate in enhancing TPA cross-section ( ) for the transition in GFPs. Furthermore, it seems that details of h-bonds network in the CRO's vicinity influences response to CRO – environment electrostatic interactions in YFPs. We postulate that engineering FPs with more hydrophilic CRO's environment can lead to greater . We also find that removing h-bonds formed with the CRO's phenolate leads to TPA enhancement for transition to higher excited states than S₁. Particularly Y145 and T203 residues are important in this regard.     

Reduction theorems for principal and classical connections

We prove general reduction theorems for gauge natural operators transforming principal connections and classical linear connections on the base manifold into sections of an arbitrary gauge natural bundle. Then we apply our results to the principal prolongation of connections. Finally we describe all such gauge natural operators for some special cases of a Lie group G.     

On geometric convergence rate of Markov search towards the fat target

Let $f:A\to \mathbb{R}$ be a continuous function with the minimal value $f^{?}$, where $A$ is the compact metric space. Let ${\left\{X_t\right\}}_{t\in \mathbb{N}}$ be a Markov chain which represents the global optimization process on $A$. We present sufficient conditions for very strong, geometric convergence mode of the form $Ef\left(X_t\right)?f^1\le c^t?(Ef\left(X_0\right)?f^1)$, where $c\in (0,1)$ is some constant. This convergence mode is natural if the set of global minima is fat.     

The effect of sample weight in thermogravimetric analysis of low viscosity polypropylene in air atmosphere

Low viscosity polypropylene is a new group of homopolymers for the manufacture of melt-blown nonwovens. The thermooxidative degradation of isotactic polypropylene was studied. Experiments using varied sample size and flow rates were undertaken to determine possible effects of these experimental parameters on the low viscosity thermo-oxidation process. It was found that the results of thermogravimetric analysis (temperature of 50%) of low viscosity polypropylene samples very strongly depend on the weight of the sample. The influence of gas flow conditions, sample pan geometry and sample melt flow rates parameters on the results of thermogravimetric analysis has not been observed.     

Molecular-scale tribology of amorphous carbon coatings: effects of film thickness,adhesion, and long-range interactions

Classical molecular dynamics simulations have been conducted to investigate the atomic-scale friction and wear when hydrogen-terminated diamond (111) counterfaces are in sliding contact with diamond (111) surfaces coated with amorphous, hydrogen-free carbon films. Two films, with approximately the same ratio of sp(3)-to-sp(2) carbon, but different thicknesses, have been examined. Both systems give a similar average friction in the load range examined. Above a critical load, a series of tribochemical reactions occur resulting in a significant restructuring of the film. This restructuring is analogous to the "run-in" observed in macroscopic friction experiments and reduces the friction. The contribution of adhesion between the probe (counterface) and the sample to friction was examined by varying the saturation of the counterface. Decreasing the degree of counterface saturation, by reducing the hydrogen termination, increases the friction. Finally, the contribution of long-range interactions to friction was examined by using two potential energy functions that differ only in their long-range forces to examine friction in the same system.     

Traveling chimera states for coupled pendula

Nonlinear Dynamics - We investigate the phenomenon of traveling chimera states in the ring of self-excited coupled pendula suspended on the horizontally oscillating wheel. The bifurcation scenario...     

Investigation of complexes of octaethyltetraamidepyrophosphate (OETAPP) with uranyl salts using infrared spectroscopy

The infrared spectra of the complexes UO₂ (NO₃)₂-octaethyltetraamidepyrophosphate (OETAPP) and UO₂ Cl₂-OETAPP were investigated to test their formation and structure. Under the experimental conditions used, a stoichiometry of 1∶1 was found for both complex types.