Investigation on corrosion inhibition and adsorption mechanism of azomethine derivatives at mild steel/0.5 ​M ​H2SO4 solution interface: Gravimetric,electrochemical, SEM and EDX studies

The inhibition performance of five azomethine derivatives such as: 1-(4-Methyloxy phenylimino)-1-(phenylhydrazono)-propan-2-one (SB₁), 1-(4-Methylphenylimino)-1-(phenylhydrazono) propan-2-one (SB₂), 1-(phenylimino)-1(phenylhydrazono)-propan-2-one (SB₃), 1-(4-Bromo phenylimino)-1(phenylhydrazono)-propan-2-one (SB₄) and 1-(4-Chlorophenylimino)-1(phenylhydrazono) -propan-2-on (SB₅) as corrosion inhibitors for mild steel in sulfuric acid 0.5 ?M were investigated using different methods. All experimental results demonstrate that these compounds are eficients inhibitors. The inhibition efficiencies ($IE$) increase with inhibitors concentration. At 7.5 $\times$ 10^?5 ?M, the $IE$ was 97.27%, 96.31%, 94.23%, 93.19 and 91.64% for SB₁, SB₂, SB₃, SB₄ and SB₅, respectively. The potentiodynamic polarization results indicated that all the studied inhibitors act as mixed type. The adsorption process on mild steel surface obeyed Langmuir isotherm. The associated activation parameters and thermodynamic have been calculated and discussed. The adsorbed film formed on the metal surface was characterized by SEM and EDX.     

A Procedure for Transforming Impedance Spectra for the Determination of Mechanism of Electrochemical Reactions

Transformation of impedance spectra into relaxation time spectra (RTS) is used for determining contributions of individual processes of the oxygen electroreduction reaction (OER) to the polarization resistance of the electrochemical cell. The transformation technique involves the solution of the convolution equation found with the aid of a modified Van Cittert iteration algorithm checked on model impedance spectra. The technique, when used to analyze impedance spectra of electrochemical cells air|Pt|YSZ|YSZ + Pt|air, shows that the conversion of a globular structure of the YSZ + Pt cermet layer to a columnar one is accompanied by a change of peak amplitudes in RTS. The revealed RTS dynamics when heated to 750°C is compared with peculiarities of individual processes in OER.     

Energy decomposition in molecular complexes: implications for the treatment of polarization in molecular simulations

This study examines the contribution of electrostatic and polarization to the interaction energy in a variety of molecular complexes. The results obtained from the Kitaura-Morokuma (KM) energy decomposition analysis at the HF/6-31G(d) level indicate that, for intermolecular distances around the equilibrium geometries, the polarization energy can be determined as the addition of the polarization energies of interacting blocks, as the mixed polarization term is typically negligible. Comparison of KM and QM/MM results shows that the electrostatic energy determined in the KM method is underestimated (in absolute value) by QM/MM methods. The reason of such underestimation can be attributed to the simplified representation of treating the interaction between overlapping charge distribution by the interaction of a QM molecule with a set of point charges. Nevertheless, the polarization energies calculated by KM and QM/MM methods are in close agreement. Finally, a consistent, automated strategy to derive charge distributions that include implicitly polarization effects in pairwise, additive force fields is presented. The strategy relies in the simultaneous fitting of electrostatic and polarization energies computed by placing a suitable perturbing particle at selected points around the molecule. The suitability of these charges to describe molecular interactions is discussed.     

荧光探针法研究可聚合有机分子(BMDM)/二苯醚的凝胶化过程

用荧光素作荧光探针 ,研究了可聚合凝胶因子 4,4′ 二 (α 甲基丙烯酰氧基 1 ,3 亚乙氧基羰基丙酰氨基 )二苯甲烷 (BMDM)在二苯醚的凝胶化过程中的聚集状态 .研究结果发现 ,与荧光素在二苯醚溶液中的荧光光谱相比 ,在凝胶中出现了 1 0～2 5nm的红移 ;而且发现分子凝胶的凝胶化时间随着BMDM浓度的增加而减小 .偏振荧光法研究分子凝胶的取向发现 ,该分子凝胶的形成过程是从各向同性的溶液(P0 =0 )向各向异性的溶胶 (P>0 )转变 ,再向各向同性的凝胶 (Pgel≈ 0 )转变的过程     

Chemical shift driven geometry optimization

A new method for refinement of 3D molecular structures by geometry optimization is presented. Prerequisites are a force field and a very fast procedure for the calculation of chemical shifts in every step of optimization. To the energy, provided by the force field (COSMOS force field), a pseudoenergy, depending on the difference between experimental and calculated chemical shifts, is added. In addition to the energy gradients, pseudoforces are computed. This requires the derivatives of the chemical shifts with respect to the coordinates. The pseudoforces are analytically derived from the integral expressions of the bond polarization theory. Single chemical shift values attributed to corresponding atoms are considered for structural correction. As a first example, this method is applied for proton position refinement of the D-mannitol X-ray structure. A crystal structure refinement with 13C chemical shift pseudoforces is carried out.     

Dynamics of photoexcited donor-acceptor complexes between C60 andN,N-diethylaniline. Polarization picosecond spectroscopy study

The kinetics of the formation and decay of photoexcited radical ion pairs of donoracceptor charge-transfer complexes between C₆₀ andN,N-diethylaniline (DEA) in chlorobenzene was studied by picosecond laser-induced diffraction gratings. It was established that the anisotropy of polarization of the diffraction signal decreases as the concentration of DEA increases. The radical ion states of the photoexcited C₆₀ ⁻...DEA⁺ complex have zero anisotropy. This effect is likely due to the isotropic intracomplex transfer of an electron from the local excited state to the radical ion state. The rate constant of quenching of the singlet excited C₆₀ byN,N-diethylaniline (1.4·10¹⁰ L mol⁻¹ s⁻¹) and the lifetimes of the solventseparated C₆₀ ⁻...DEA⁺ and tight [C₆₀ ⁻...DEA⁺] (95±7 and 31±4 ps, respectively) radical ion pairs were measured. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1605–1610, September, 1997.     

Dielectric analysis of polystyrene microcapsules using scanning dielectric microscope

 A dielectric imaging technique with a scanning dielectric microscope was applied to polystyrene microcapsules in an aqueous environment to study the electrical properties of individual ones. The dielectric images obtained over a frequency range from 10 kHz to 10 MHz showed frequency dependence, which indicated dielectric dispersion (or relaxation) due to interfacial polarization or the build up of charge on the boundaries between the microcapsule shell and the aqueous phases. The dielectric dispersion was analyzed based on an equivalent electrical circuit model and a shell-sphere model in which a spherical core is covered with an insulating shell. Received: 26 September 1997 Accepted: 26 December 1997     

Dissociation of photochromic spiroanthrooxazine dimers in the excited state

The influence of temperature and concentration on the spectral polarization properties of the luminescence and absorption of molecules of the original form of photochromic spiroanthrooxazine (SAO) in petroleum ether and polyethylene was investigated. It was shown that the long-wave part of the absorption spectra of the molecules is formed by at least two -*-type electronic transitions, the oscillators of which are mutually orthogonal. It is suggested that the SAO molecules form dimers in nonpolar media through dipole-dipole interaction, and at high concentrations they also form higher associates. Dimers stable in the ground state dissociate when excited to the second electronic transition with a rate constant of 10¹²–10¹³ s^–1.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Department of the Institute of Solid-State Physics and Semiconductors, Academy of Sciences of Belarus, 211177 Vitebsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 99–106, January, 1992.     

Inclusion of dynamic σ-π polarization in π-electronab initio calculations

Summary A method is presented, whereby dynamic - polarization, i.e. the correlation effect expressed by simultaneous (-*, -*) excitations, can be approximately included in a multi-reference configuration interaction (MRCI) or multi-configurational self-consistent field (MC-SCF) calculation, without need to explicitly correlate the sigma orbitals. The method, which we call the capacitance matrix method, is based on the use of conventional one-electron integrals, from which a polarization potential (SPP) contribution is computed and added to the one- and two-electron Hamiltonian. In the present form, the method requires one parameter for each type of atom, and one for each type of bond. These parameters were adjusted to reproduce the dynamic - polarization energy, computed by restricted multi-reference CI calculations, of a number of states of different hydrocarbons, and the agreement was within a few percent. Using the same parameters in CAS (Complete Active Space) SCF calculations of various states of benzene gives excitation energies, when SPP is included, which is comparable to those obtained by much more elaborate MRCI calculations.