The geometries of one-electron reduced/oxidized species ([TOP]/[VOP]) of vanadyl porphyrin (VOP) have been calculated with PBE1PBE method. The results show that for both [VOP]− and [VOP] the ground states are triplet, in which one of the two unpaired electron occupies the dxy orbital of the V atom while the other occupies the π-orbital of porphyrin ring. Thus both [VOP]− and [VOP] can be consid...

A combined theoretical and experimental study was performed on diarylethenes and diarylethene-capped sexithiophenes aiming at an improved understanding of the electrochemical and photochemical ring-opening and ring-closing mechanisms. Theoretical calculations, based on DFT and TDDFT, suggested that the spatial distribution and the occupancy of the frontier orbitals determine and control the dia...

We herein present the results of a series of calculations performed on some representative cluster models of hybrid organic-inorganic halide perovskites, (MA)jPbkXl (l = 2j + k; MA = methylammonium, +CH3NH3; X = halide). In particular, aimed at finding possible analogies with the bulk, we focused our initial attention on neutral clusters of iodides (X = I) constituted by an increasing number of...

The crystal and molecular structures of three new thiosemicarbazones, 2-[1-(2-hydroxy-5-methoxyphenyl)ethylidene]-N-methyl-hydrazinecarbothioamide monohydrate (1), 2-[1-(2-hydroxy-5-methoxyphenyl)ethylidene]-N-ethyl-hydrazinecarbothioamide (2) and 2-[1-(2-hydroxy-4-methoxyphenyl)ethylidene]-N-ethyl-hydrazinecarbothioamide acetonitrile solvate (3), are reported and confirmed by single crystal X-...

In the present study, structural properties of 2-[(1H-benzimidazol-2-ylmethyl)-amino]-benzoic acid methyl ester have been studied extensively by spectral methods and X-ray crystallography. Quantum mechanical calculations of energies, geometries, vibrational wavenumbers, NMR and electronic transitions were carried out by DFT using B3LYP functional combined with 6-31G(d) basis set. Natural bond o...

We address the nature of the bond between water molecules and metal surfaces through a systematic density-functional theory (DFT) study of H(2)O monomer adsorption on a series of close-packed transition metal surfaces: Ru(0001), Rh(111), Pd(111), and Ag(111). Aiming to understand the origin behind energetic and structural trends along the 4d series we employ a range of analysis tools such as th...

The spectrum-detected smallest sulfide clusterfullerene Sc2S@C68 has not been characterized yet. Herein, we explored a series of Sc2S@C68 species to determine which could be the most promising isomer. The results suggest that a sulfide cluster encapsulated in the C2v(6073)-C68 cage which violates the isolated pentagon rule (IPR) with two opposite pentalenes has the lowest energy and an overwhel...

A physical model of electronic effects in the QSAR of benzene derivatives, together with a regression technique for finding predictive equations, is presented. The model is simple, based on the quantum theoretic description of the benzene molecule, and accounts for the variance in activity of hallucinogenic phenylalkylamines as well as a classical description in terms of electronic (atomic char...

Bonding in the bis(pentalene)dititanium "double-sandwich" species Ti2Pn2 (Pn = C8H6) and its interaction with other fragments have been investigated by density functional calculations and fragment analysis. Ti2Pn2 with C2v symmetry has two metal-metal bonds and a low-lying metal-based empty orbital, all three frontier orbitals having a1 symmetry. The latter may be regarded as being derived by s...

We developed a new reaction simulator, "LUMMOX." It is an intermolecular interaction analyzer based on the theories of paired interacting orbitals (PIOs) and localized frontier orbitals (LFOs) that have been developed by Fujimoto et al. (Fukui, K.; Koga, N.; Fujimoto, H. J Am Chem Soc 1981, 103, 196; Fujimoto, H.; Koga, N.; Fukui, K. J Am Chem Soc 1981, 103, 7452; Fujimoto, H.; Satoh, S. J Phys...