Direct observation of the intermediate in an ultrafast isomerization.

Using a combination of two-dimensional infrared (2D IR) and variable temperature Fourier transform infrared (FTIR) spectroscopies the rapid structural isomerization of a five-coordinate ruthenium complex is investigated. In methylene chloride, three exchanging isomers were observed: (1) square pyramidal equatorial, (1); (2) trigonal bipyramidal, (0); and (3) square pyramidal apical, (2). Exchange between 1 and 0 was found to be an endergonic process (ΔH = 0.84 (0.08) kcal mol-1, ΔS = 0.6 (0.4) eu) with an isomerization time constant of 4.3 (1.5) picoseconds (ps, 10-12 s). Exchange between 0 and 2 however was found to be exergonic (ΔH = -2.18 (0.06) kcal mol-1, ΔS = -5.3 (0.3) eu) and rate limiting with an isomerization time constant of 6.3 (1.6) ps. The trigonal bipyramidal complex was found to be an intermediate, with an activation barrier of 2.2 (0.2) kcal mol-1 and 2.4 (0.2) kcal mol-1 relative to the equatorial and apical square pyramidal isomers respectively. This study provides direct validation of the mechanism of Berry pseudorotation - the pairwise exchange of ligands in a five-coordinate complex - a process that was first described over fifty years ago. This study also clearly demonstrates that the rate of pseudorotation approaches the frequency of molecular vibrations

Evaluation of electric and magnetic fields distribution and SAR induced in 3D models of water containers by radiofrequency radiation using FDTD and FEM simulation techniques

In this study, two software packages using different numerical techniques FEKO 6.3 with Finite-Element Method (FEM) and XFDTD 7 with Finite Difference Time Domain Method (FDTD) were used to assess exposure of 3D models of square, rectangular, and pyramidal shaped water containers to electromagnetic waves at 300, 900, and 2400 MHz frequencies. Using the FEM simulation technique, the peak electric field of 25, 4.5, and 2 V/m at 300 MHz and 15.75, 1.5, and 1.75 V/m at 900 MHz were observed in pyramidal, rectangular, and square shaped 3D container models, respectively. The FDTD simulation method confirmed a peak electric field of 12.782, 10.907, and 10.625 V/m at 2400 MHz in the pyramidal, square, and rectangular shaped 3D models, respectively. The study demonstrated an exceptionally high level of electric field in the water in the two identical pyramid shaped 3D models analyzed using the two different simulation techniques. Both FEM and FDTD simulation techniques indicated variations in the distribution of electric, magnetic fields, and specific absorption rate of water stored inside the 3D container models. The study successfully demonstrated that shape and dimensions of 3D models significantly influence the electric and magnetic fields inside packaged materials; thus, specific absorption rates in the stored water vary according to the shape and dimensions of the packaging materials.Comment: 22 pages, 30 figures and 2 table

Studies of Histidine, Phenylalanine Complexes of Oxovanadium(IV) Derived from Acetylacetone

Schiff base complexes of oxovanadium(IV) with amino acids and acetylacetone were synthesized and characterized by elemental analysis, conductivity measurements, spectral and magnetic data. The complexes were found to be non-electrolytes and stoichiometry shown 1:1. The spectral and magnetic data were suggesting the square pyramidal geometr

Spectral properties of the two-dimensional Schrödinger Hamiltonian with various solvable confinements in the presence of a central point perturbation

We study three solvable two-dimensional systems perturbed by a point interaction centered at the origin. The unperturbed systems are the isotropic harmonic oscillator, a square pyramidal potential and a combination thereof. We study the spectrum of the perturbed systems. We show that, while most eigenvalues are not affected by the point perturbation, a few of them are strongly perturbed. We show that for some values of one parameter, these perturbed eigenvalues may take lower values than the immediately lower eigenvalue, so that level crossings occur. These level crossings are studied in some detail

Diiodido[4′-(4-pyrid­yl)-2,2′:6′,2′′-terpyridine-κ3 N,N′,N′′]copper(II)

The CuII atom in the title compound, [CuI2(C20H14N4)], has a distorted square-pyramidal coordination formed by the N atoms of the tridentate 4′-(4-pyrid­yl)-2,2′:6′2′′-terpyridine (pyterpy) ligand and two I atoms; one of the I atoms is in the apical position. In contrast to other known square-pyramidal diiodido- and dibromidocopper complexes of the pyterpy ligand in which metal–halogen distances are significantly different, in the title compound the apical and equatorial Cu—I bonds are almost identical [2.6141 (8) and 2.6025 (8) Å, respectively]

trans-Chlorido{3-chloro-2-[(1-naphth­yl)imino­meth­yl]phenyl-κ2 C 1,N}bis­(trimethyl­phosphane)nickel(II)

The title compound, [Ni(C17H11ClN)Cl(C3H9P)2], was obtained as a product of the reaction of [Ni(PMe3)4] with a molar equivalent of 2,6-dichloro-N-naphthyl­benzaldehyde­amine in diethyl ether. The τ parameter is 0.3, indicating that the coordination geometry is square-pyramidal. The NiII atom lies in the center of a square pyramidal in which one C, one Cl and two P atoms form the basal plane, with the imine N atom in an apical position. Two P-atom donors are located in trans positions

Investigation of a square-based pyramidal-sheet roof

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