Narrow Results

Molecular orbital (MO) calculations of more than 60 porphyrinic π conjugated structures have been performed within the framework of the Pariser–Parr–Pople approximation. The results of a series of compounds are introduced and summarized in order to show how they vary depending on the systematic change in molecular structure. These are shown schematically or itemized. Our results are compared with the spectra of the corresponding known compounds and with the MO results reported by previous workers, if available. In addition, the results have continually been compared, where possible, with those of tetraazaporphyrin or phthalocyanine systems. In naphthalene- or anthracene-fused compounds, these molecule-centered orbitals often appear, and these are indicated using either triangles or circles in figures if they appear between HOMO – 3 and LUMO + 3 orbitals.

A Lorentz and gauge symmetry preserving regularization method has been proposed recently in four dimensions based on Euclidean momentum cutoff. It is shown that the triangle anomaly can be calculated unambiguously with this new improved cutoff. The anticommutator of γ⁵ and γ^μ multiplied by five γ matrices is proportional to terms that do not vanish under a divergent loop-momentum integral, but cancel otherwise.

The trimethylamine-catalyzed Baylis–Hillman reaction of formaldehyde and vinylaldehyde has been studied with the density functional theory (DFT) method of B3LYP/6-31+G(d,p). In the gas phase, the reaction involves an amine–formaldehyde–vinylaldehyde trimolecular addition transition structure followed by rate-determining intramolecular 1,3-hydrogen shift. When a bulk solvent effect of water was considered with conductor-like polarizable continuum model (CPCM), the reaction was found to follow the sequence of Michael-addition of amine to vinylaldehyde (step 1), addition of formaldehyde (step 2), and 1,3-hydrogen shift (step 3), with the 1,3-hydrogen shift as rate-determining. The overall reaction barrier is significantly reduced. When a molecule of water is involved in the reaction, the 1,3-hydrogen shift is significantly promoted so that the rate-determining step becomes the C–C bond formation. The calculated overall reaction barrier is in agreement with experimental observations.

In this work, calculations of pK_b values have been performed for aniline and its substituted derivatives and sulfonamide drugs by using Gaussian 98 software package. Gas-phase energies were calculated with HF/6-31 G** and B3LYP/6-31 G** levels of theory. Free energies of solvation have been computed using the polarizable continuum model (PCM), conductor-like polarizable continuum model (CPCM) and the integral equation formalism-polarizable continuum model (IEFPCM) at the same levels which have been used for geometry determination in the gas-phase. The results show that the calculated pK_b values using the B3LYP/6-31 G** are better than those using the corresponding HF/6-31 G**. At first, the correlation equation was found to determine the pK_b values of the investigated anilines. Then, this correlation equation was used to calculate the pK_b values of the sulfonamide drugs. The results obtained indicate that the PCM model is a suitable solvation model for calculating pK_b values in comparison to the other solvation models. For the investigated compounds a good agreement between the experimental and the calculated pK_b values was also observed.

In this review, we have mainly shown the recent computational studies on formic acid adsorption and selective dissociation to produce hydrogen (HCOOH → CO₂ + H₂) on several metal (Pt, Pd, Ni, Cu, Rh and Au) and metal oxide (TiO₂, MgO, ZnO and NiO) surfaces, and both thermal decomposition and electro-catalytic oxidation have been discussed. The decomposition mechanisms of formic acid have been studied by using different computational models and methods, not only interesting and exciting but also different and controversial results have been reported. It is noted that the model systems used in these studies are too simple and idealized, and they cannot represent the real catalysts or the catalytic systems, and more sophisticated computational methodologies and real model systems under the consideration of the working conditions are therefore needed.

Eight strongly electron-donating alkylthio- or arylthio-groups have been introduced to a strongly electron-withdrawing pyrazinoporphyrazine (PyZ) core, to form the Zn complexes of octadecylthiolated ZnPyZ, (SDc)${}_8$ZnPyZ, and octaphenylthiolated ZnPyZ, (S$\mathrm{\Phi }$)${}_8$ZnPyZ, and their electronic structures studied by ¹H NMR and electronic absorption spectroscopy. The strength of the ring current, aromaticity, and flow of charge were discussed by calculating the ring current, nucleus-independent chemical shift (NICS), and anisotropy of the current-induced density (ACID), respectively. Good agreement was seen for the results of these three calculations, demonstrating that a strong ring current of the macrocycle is produced when the aromatic ring fused to the tetraazaporphyrin core has a weaker diamagnetic ring current, $i.e$. weaker aromaticity (negatively smaller NICS values). TD-DFT molecular orbital (MO) calculations succeeded in explaining the differences of the absorption spectra between these octathiolated ZnPyZs and those without thiolated groups. The singlet oxygen quantum yield in pyridine (0.62) of (S$\mathrm{\Phi }$)${}_8$ZnPyZ was similar to that (0.61) of normal ZnPc.

Isoindole-diimine, which can be obtained by bubbling ammonia gas into a solution of phthalonitrile derivatives in the presence of Na${}^{+}$ ion, is a final and best precursor for phthalocyanine synthesis. In this study, isoindole-diimine and various derivatives have been prepared without bubbling ammonia gas using in situ generated ammonia that was produced from formamide and a strong alkali such as NaOH and NaNH₂. A longer reaction time, higher temperature, and larger amount of formamide were required for phthalonitrile derivatives with electron-donating groups, but this method is recommendable in that an NH₃ gas cylinder and concomitant gas regulator, which are not inexpensive, are not required. Attempts were made to interpret the IR and absorption spectra of the resultant diimines. The signals due to imino proton or N-H of diimino compounds were experimentally found to appear at around 8.2$\sim$9.5 ppm in ¹H-NMR and ca. 3500–3000 cm${}^{-1}$ in IR spectra.