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Oxidative-denitrogenation (ODN) of indole (IND) and methyl-substituted INDs (methyl-INDs), representative neutral nitrogen-containing compounds (NCCs), was carried out with TiO2@C and H2O2 as heterogeneous catalyst and oxidant, respectively, under ultrasound irradiation. The oxidation of INDs progressed through radical formation, as evidenced by electron spin resonance and radical scavenger experiments. The oxidized position of INDs in the ODN process was checked via characterization of the obtained products. It was observed that the oxidation finally occurred on the carbon rather than on the nitrogen atom of INDs, unlike the oxidation of basic NCCs (e.g., oxidation on the nitrogen atom, as respective N-oxides were formed) and sulfur-containing compounds. To understand the relative reactivity and oxidation position, electron density (ED) on the nitrogen atom of the studied INDs and relative stability of representative intermediates/products were calculated. It could be confirmed that ED on the nitrogen atom of the INDs is very important in the oxidation of INDs since the ODN reactivity of INDs was enhanced with increasing ED on the nitrogen atom of the investigated INDs. Moreover, theoretical analyses of the relative stability of substrate and intermediates/products (especially for IND) can explain the route for the observed final products in ODN. In other words, oxygen on the nitrogen atom, obtained via the first step of oxidation (electrophilic addition of an active oxygen atom on nitrogen), moves to the nearby carbon atom, because of the relative stability of the intermediates and products. [ABSTRACT FROM AUTHOR]

The non-relativistic and relativistic potential energy surfaces (PESs) of the symmetric and asymmetric reaction paths of Si(100)-2×1 oxidations by atomic oxygen were theoretically explored. Although only the singlet PES turned out to exist as a major channel leading to 'on-dimer' product, both the singlet and triplet PESs leading to 'on-top' products are attractive. The singlet PESs leading to the two surface products were found to be the singlet combinations (open-shell singlet) of the low-lying triplet state of surface silicon dimer and the ground 3P state of atomic oxygen. The triplet state of the 'on-top' product can also be formed by the ground singlet state of the surface silicon dimer and the same 3P oxygen. The attractive singlet PESs leading to the 'on-dimer' and 'on-top' products made neither the intersystem crossings from triplet to singlet PES nor high energy 1D of atomic oxygen necessary. Rather, the low-lying triplet state of surface silicon dimer plays an important role in the initial oxidations of silicon surface. [ABSTRACT FROM AUTHOR]

The surface reaction pathways of isoxazole and oxazole on Si(100)-2 × 1 surface were theoretically investigated. They both form a weakly bound Si-N dative bond adduct on Si(100)-2 × 1 surface. In the case of isoxazole, the barrierlessly formed Si-N adduct is the most important surface product, that cannot be easily converted into other species. On the other hand, a facile concerted [4+2]CC cycloaddition without involving the initial Si-N dative bond adduct was also found in the case of oxazole adsorption. The existence of Diels-Alder reactions is attributed to the particular arrangement of the two heteroatoms of oxazole in such a way that the two Si-C σ-bonds can be formed in a [4+2] fashion. In short, the unique geometric arrangements and electronegativity of these similar heteroatomic molecules yielded distinctively different surface reaction characteristics. [ABSTRACT FROM AUTHOR]

The thermal decomposition reactions of methylamine, ethylamine, and 1-propylamine absorbed on Si(100)-2 × 1 surface were theoretically investigated. Eight decomposition channels were found leading to desorption products of imine, H2, alkyl cyanide, ammonia, aziridine, alkene, azetidine, and cyclopropane, which supports the experimental assignments. Our mechanistic studies strongly suggest that the alkyl cyanide (hydrogen cyanide in the case of methylamine) channel is coupled with the hydrogen desorption step. The β-hydrogen of ethylamine and 1-propylamine was found to undergo additional decomposition reactions producing aziridine and alkene, which were classified as γ- and β-eliminations, respectively. It was also found that the γ-hydrogen of 1-propylamine undergoes azetidine and cyclopropane producing decompositions, which were classified as δ- and γ-eliminations. In general, γ- and δ-hydrogen involved decomposition reactions are kinetically less favorable than β-hydrogen involved ones. Consequently, it is expected that the thermal decompositions of the primary alkyl amines with longer alkyl chains would not add additional favorable decomposition channels. Except alkyl cyanide and ammonia desorption channels, the decompositions occur in a concerted fashion. [ABSTRACT FROM AUTHOR]

Multireference as well as density functional theories in combination with the surface integrated molecular orbital molecular mechanics were adopted to study the surface reactions of cyanogens on Si(100)-2×1 surface. Three different products were identified as minima in the initial surface reaction. Among these, the [2+2] product is both kinetically easily accessible and thermodynamically the most stable. Therefore, it can be considered as the experimentally found strongly bound surface species. Unlike other conjugated systems, the [4+2] product is less stable than the [2+2] product. Subsequent surface isomerization studies revealed that kinetically favorable channels exist between the initially formed low-temperature species and the high-temperature species, indicating that surface morphology changes gradually as a function of surface temperature. Theses two channels eventually lead to the same final surface products, which is consistent with experiment. Current study shows that the subsequent surface isomerizations are the key reactions to better understand the complex surface structures and their properties. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Multireference as well as single-reference wave functions were adopted to study the surface reaction mechanisms of hydrazine. The initial surface mechanisms resemble those of ammonia and its methyl derivatives. MRMP2 values indicate that the lifetime of initial molecularly adsorbed species should be longer than previously suggested. High energy path as well as low energy path of subsequent surface reactions were found. The theoretical initial surface product of low energy path is consistent with the experimentally suggested structure. Both paths eventually lead to very stable surface products, which are also consistent with the experimentally suggested structures. The reaction channels of the experimentally observed NH[sub 3] desorptions were also revealed. It was shown that the high reactivity of hydrazine as compared to ammonia and its methyl derivatives is due to the high nucleophilic ability of the additional nitrogen atom of hydrazine. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Photodecomposition of cyclopropanone is investigated by static quantum chemical calculations and non-adiabatic molecular dynamics (NAMD) simulations. The quantum chemical calculations are carried out by an ensemble density functional theory (eDFT) method capable of delivering high quality results for the ground and excited electronic states of molecules with dissociating bonds. In the NAMD simulations, this method is combined with a novel trajectory surface hopping (TSH) methodology derived from the exact factorization of the electronic-nuclear wavefunction. An ultrafast biexponential decay of the S1 state of cyclopropanone is predicted, where the short (ca. 30 fs) decay time is due to the trajectories reaching the conical intersection (CI) seam on the first approach and the long (ca. 120 fs) decay time is due to recrossing of the CI seam. The experimentally observed dependence of the dissociation (C3H4O* → C2H4 + CO) quantum yield on the excitation wavelength is correctly reproduced by the NAMD simulations. The dependence is explained by the necessity to excite certain vibrational normal modes (e.g., a ring stretching mode with the frequency of 769 cm−1) to break a lateral C–C bond remaining intact at the geometries of the CI seam. [ABSTRACT FROM AUTHOR]

This paper reports two related studies of the Form II → Form I crystal-crystal transformation in isotactic polybutene-1. First, it was found that in melt spun filaments, the rate of [...]

A study of structure development in thin melt spun isotactic polypropylene filaments is described, which is then applied to the prediction of the behavior of thick parts. Conditions under which [...]

It has been assumed that all conjugated annulenes satisfying the Huckel 4n + 2 rule, apart from benzene. Large annules have recently been calculated using MNDOC, revealing that (18)annulene the aromatic Dsub6h structure is more favourable, but the (30)annullene Dsub6h structure is less stable than a bond localized Dsub3h structure. (14)annulene and (18)annulene have been studied with HF/6-311G, BLYP/6-311G, B3LYP/6-311G and MP2super15/6-31G methods to determine potential energy surface on the delta coordinate.