On the mechanism of proton transfer in imidazole

The force fields, in-plane vibrations, and relative intensities of Raman spectra have been calculated and analyzed for the N₁H and N₃H tautomers of imidazole, imidazolium cation, and their model structures. The results obtained for the isolated state of imidazole correspond to the intramolecular mechanism of proton transfer.     

由NO分子从头计算结果和紫外光电子能谱确定NO的分子结构

对于NO分子轨道的能级次序现有两种不同的说法,不少人根据NO与O_2~+是等电子体,由O_2~+分子的能级次序确定NO分子组态。本文用NO和O_2~(+)从头计算结果以及NO的紫外光电子能谱相结合的方法说明NO的5σ轨道是弱成键轨道,5σ的轨道能稍高于1π轨道能,也就是说NO的能级次序是与N_2分子相同的;NO与O_2~+虽是等电子体,但是能级次序并不相同,因此由O_2~+的能级次序确定NO分子的电子组态是不妥的。     

Reflection of electrons and photons from solids bombarded by 0.1 - to 100-MeV electrons

Electron and photon reflection ratios (in number and energy) for absorbers bombarded by electrons have been computed with the ITS Monte Carlo system version 3. Electrons of energies from 0.1 to 100 MeV have been assumed normally incident on an effectively semi-infinite absorber. The absorbers considered are elemental solids of atomic numbers from 4 to 92. The data on the electron reflection ratios agree rather well with the experimental data collected from literature except some discrepancies when the number-reflection ratio is small. For photons, the number-reflection ratio increases with increasing energy, but the energy-reflection ratio shows a maximum around 10 MeV. Empirical equations for the electron reflection ratios and the photon energy-reflection ratio are given (for electrons, graphs only).     

Exploring high pressure structural transformations,electronic properties and superconducting properties of MH2 (M = Nb,Ta)

The high-pressure structures and properties of MH₂ (M = Nb, Ta) are explored through an ab initio evolutionary algorithm for crystal structure prediction and first-principles calculations. It is found that NbH₂ undergoes a phase transition from a cubic Fm$\overline{3}$m structure with regular NbH₈ cubes to an orthorhombic Pnma structure with fascinating distorted NbH₉ tetrakaidecahedrons at 48.8 GPa, while the phase transition pressure of TaH₂ from a hexagonal P6₃mc phase with slightly distorted TaH₇ decahedron to an orthorhombic Pnma phase with attractive distorted TaH₉ tetrakaidecahedrons is about 90.0 GPa. Besides, the calculated electronic band structure and density of states demonstrate that all of these structures are metallic. The Poisson’s ratio, electron localization function, and Bader charge analysis suggest that these phases possess dominant ionic bonding character with the effective charges transferring from the metal atom to H. From our electron–phonon calculations, the calculated superconducting critical temperature T_c of the Pnma-NbH₂ is 6.903 K at 50 GPa. Finally, via the quasi-harmonic approximation method, the phase diagrams at pressure up to 300 GPa and temperature up to 1000 K of MH₂ (M = Nb, Ta) are established, where the transition pressure of Fm$\overline{3}$m-NbH₂ → Pnma-NbH₂ and P6₃mc-TaH₂ → Pnma-TaH₂ were found to decrease with increasing temperature.     

Numerical examination of performance of some exchange-correlation functionals for molecules containing heavy elements

The performance of 17 exchange-correlation functionals for molecules containing heavy elements are numerically examined through four-component relativistic density DFT calculations. The examined functionals show the similar accuracy as they do for the molecules containing light elements only except for bond lengths. LDA and OP86 produce good results for bond lengths and frequencies but bad bond energies. Different functionals do not show much different performance for bond energies except LDA. BP86 and GP86 produce results with average accuracy while LYP does not perform well. Although encouraging results are obtained with functional B97GGA-1, other heavily parameterized and meta-GGA functionals do not produce impressive results.     

Rotational barrier for 1-acetyl-2-(p-methoxy benzyl)-3-pyrroline

Calculation of the rotational barriers for the trans- and cis-forms of 2-(p-methoxy)-1-acetyl-pyrroline are presented in this paper. It is found that thetrans-isomer is slightly more favourable energetically, while the rotations of the cis-form are highly impeded. Hence the relevant rotations are in thetrans-form which stabilizes its energy by forming a weak inner proton bond between the carbonyl oxygen and the pyrroline ring. The acetyl rotational barrier is of the order of 8 kcal, which is well in accord with experimental data reported in the literature for other acetyl-amide derivatives.[/p]Work supported in part by Instituto Mexicano del Petróleo.     

Evaluation of dead time calculation in liquid chromatography using a linearization procedure for homologous series

A mathematical method for the calculation of the dead time (t_m) in HPLC was evaluated using a computer simulation approach, in which artificial perturbations were introduced to Simulated homolog retention times. The calculation was based on a modified and extended Grobler and Bálisz (GB) method. Investigated wav how the precision of the calculated t_M is affected by: statistical fluctuations in retention times and which, and how many homolog retention times are used. Based on these simulations a two-step procedure for the t_M calculation is proposed: In the first step the linearity of log t_{R, n} vs carbon number n is checked using as many homolog retention times as possible. The slope value b^o of the first linear regression in the GB method is used for the selection of homolog retention times in the final t_M calculation. In the second step the optimal selection of homologs is made and the final t_M calculation is carried out. Guidelines for homolog selection are given.     

Fragment methods for IR spectrum calculations of organophosphorus compounds

For highly toxic organophosphorus compounds on the limiting lists of the International Chemical Weapons Ban Treaty, fragment methods may be used for calculating their IR vibrational spectra; this is shown for O-alkyl alkylfluorophosphonates used as examples. The geometrical parameters and the parameters of the potential and electrooptic functions are found for the major fragments of these compounds. Due to this, fast predictive computation of IR spectra of O-alkyl alkylfluorophosphonates is possible, the accuracy of calculation being sufficient for spectral identification of these compounds; a database of the calculated IR spectra may be created.     

Alkylation of cobalt and lutetium tetra(3,5-di-tert-butyl-4-hydroxyphenyl)dodecachlorophthalocyanine complexes initiated with current

Electrochemical properties of tetra(3,5-di-tert-butyl-4-hydroxyphenyl)dodecachlorophthalocyanine complexes of cobalt(II) and lutetium(III) in DMF solutions have been studied. It was suggested that in the presence ofn-butyl bromide, the electrochemically generated monoanionic complexes undergo alkylation at the metal atom. The geometries of the neutral and anionic complexes were calculated by the ZINDO/I semiempirical method. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 289–293, February, 1998.