Ground-state and some excited states of Li2 by the half-projected Hartree–Fock method

The half-projected Hartree–Fock wave function (HPHF ) is one of simplest models for introducing some electronic correlation effects. In this model, the wave function is built up with only two Slater determinants. This simple form suggests its application for the direct determination of singlet excited states. On the other hand, because the HPHF model does not mix singlet and triplet states with M_s = 0, it can be used for determining independently singlet and triplet states without any mutual contamination. In the present work, we applied this model to determine nine electronic states of the lithium molecule; one of them exhibits even the same symmetry of the fundamental one. For this purpose, the 6-311G (d) basis was used. Potential energy curves were determined and some spectroscopic constants derived. The numerical results were compared with the available experimental data, as well as with other theoretical values. © 1995 John Wiley & Sons, Inc.     

An Analytical Method for the Separation and Determination of As(III) and As(V) in Seepage and Acid Mine Drainage Water

To avoid changes in the original As species distribution in natural water after sampling, a method of immediate separation of As(V) by anion exchange at the sampling site was developed. The procedure consists of two steps. The total concentration of arsenic is determined in one part of the water sample acidified on site. Another part of the water samples is pressed through a column filled with an anion exchanger. The As(III) species that is not redox-stable remains in the effluent of the sorbents column and can be analyzed with conventional methods after stabilization by addition of conc. HNO₃. As(V) is sorbed by the exchanger material. The As(V) concentration can be calculated as the difference between As_sol and As(III), neglecting very low contents of methylated species. Oxidation of Fe(II) by air followed by co-precipitation of arsenic with iron hydroxide was applied in field experiments to minimize the As concentration in seepage and mining water.     

Application of PM-IRRAS to study thin films on industrial and environmental samples

Polarization modulation–infrared reflection absorption spectroscopy (PM-IRRAS) was employed to analyze two unique samples: (1) an industrially prepared alkoxysilane-pretreated aluminum alloy (AA6111) in the absence and presence of a ～600-nm-thick lubricant coating and (2) a chemical warfare agent simulant, triethyl phosphate (TEP), on glass. For the pretreated aluminum samples, PM-IRRAS spectra were analyzed for three distinct regions; the SiO stretching vibration around 1120 cm^?1, the NH₂ bending mode at ～1600 cm^?1 and the CH stretching region around 2900 cm^?1. Our results showed that increasing the curing temperature (from 55 to 100 °C) improved the overall extent of cross-linking within the siloxane network. In addition, the spectra of lubricant (top coating) and the underlying siloxane layer for the aluminum samples with lubricant were collected for the same sample. Our results show that the nature of the siloxane film remains intact and unaltered after deposition of the lubricant top-coat. For detection of TEP on glass, the band at 1268 cm^?1, corresponding to the P═O vibration, was monitored. A droplet of TEP solution in dichloromethane was deposited on glass. After solvent evaporation had occurred, the intensity of the P═O vibration band was used to construct calibration curves to determine the experimental limit of detection, which was found to be ～200 μg for TEP on glass.

Kinetics of radical‐molecule reactions in aqueous solution: A benchmark study of the performance of density functional methods

The performance of 18 density functional approximations has been tested for a very challenging task, the calculations of rate constants for radical‐molecule reactions in aqueous solution. Despite of the many difficulties involved in such an enterprise, six of them provide high quality results, and are recommended to that purpose. They are LC‐ωPBE, M06‐2X, BMK, B2PLYP, M05‐2X, and MN12SX, in that order. This trend was obtained using experimental data as reference. The other relevant aspects used in this benchmark are: (i) the SMD model for mimicking the solvent; (ii) the conventional transition state, the zero‐curvature tunneling correction, and the limit imposed by diffusion for the calculation of the rate constants. Even though changing any of these aspects might alter the trend in performance, at least, when using them, the aforementioned functionals can be successfully used to obtain high quality kinetic data for the kind of reactions investigated in this work. © 2014 Wiley Periodicals, Inc.     

Computational design of rasagiline derivatives: Searching for enhanced antioxidant capability

A set of new rasagiline derivatives is presented. They were designed to be antioxidant compounds with the potential to be used for treating neurodegenerative disorders. They are expected to be multifunctional molecules that can help reduce oxidative stress, which is thought to contribute to neurodegenerative disorders. The CADMA-Chem computational protocol was used to produce rasagiline derivatives and to evaluate their likeliness as oral drugs and antioxidants. Three of them were identified as the most promising ones. They are proposed to be better free radical scavengers than rasagiline. In addition, they are expected to keep the parent's molecule neuroprotective capability. Hopefully, the results presented here would promote further experimental and theoretical investigations on these compounds.     

土壤的光谱特征及氮含量的预测研究

应用近红外光谱分析技术(NIR)测定土壤参数具有快速、方便的特点.文章分析了不同含水率、不同颗粒大小的土壤样本在不同测试角、不同测试高度对土壤光谱的影响,并得到了不同含水率和不同粒径土壤的含氮量预测模型.研究了这些因素对含氮率测量的影响,分析了NIR技术在田间实地应用预测的可能性.研究表明,光谱仪在距土壤高度为100 mm,测试角为45°时,具有最大的吸光度.土壤粒径和含水率这2个参数明显影响,当粒径在0.5～5 mm变化时,含氮量预测相关系数r为0.81左右,当土壤粒径在＜0.25和＞5 mm模型的预测能力变差.当土壤样品呈天然潮湿状态时,氮的预测结果较差.而样品干燥以后,预测相关系数较高.为土壤原位光谱测试提供了依据.     

Theoretical study on the chemical fate of adducts formed through free radical addition reactions to carotenoids

It is well known that free radicals are responsible for oxidative stress and cause numerous health disorders. As a result, the study of molecules that can scavenge free radicals is significant. One of the most important classes of free radical scavengers are carotenoids (CAR). In this work, the effectiveness of the CAR in terms of the radical adduct formation (RAF) reaction is studied using density functional theory calculations (in polar and non-polar environments). The reactions between four CAR [β-carotene (BC), zeaxanthin (ZEA), canthaxanthin (CANTA) and astaxanthin (ASTA)] with eight different radicals (^?OH, ^?OOH, ^?CH₃, ^?O–CH₃, ^?OO–CH₃, ^?SH, ^?O–CH₂–CH=CH₂, and ^?OO–CH₂–CH=CH₂), as well as substantial further reactions involved in the radical chain propagation, are analyzed. According to our results, the RAF reactions are controlled to a larger extent by the nature of the free radical than by the particular CAR they are reacting with. Thermochemistry calculations predict that each CAR molecule is able to scavenge at least two free radicals, which would lead to the termination of the radical chain process. Epoxy and diepoxy CAR species can be formed, being epoxy molecules as good free radical scavengers as their parent CAR. ASTA and CANTA are predicted to be less reactive, when reacting through RAF mechanism, than BC and ZEA.     

Quantum chemical and conventional TST calculations of rate constants for the OH + alkane reaction

Reactions of OH with methane, ethane, propane, i-butane, and n-butane have been modeled using ab initio (MP2) and hybrid DFT (BHandHLYP) methods, and the 6-311G(d,p) basis set. Furthermore, single-point calculations at the CCSD(T) level were carried out at the optimized geometries. The rate constants have been calculated using the conventional transition-state theory (CTST). Arrhenius equations are proposed in the temperature range of 250–650 K. Hindered Internal Rotation partition functions calculations were explicitly carried out and included in the total partition functions. These corrections showed to be relevant in the determination of the pre-exponential parameters, although not so important as in the NO₃ + alkane reactions [G. Bravo-Pérez, J.R. Alvarez-Idaboy, A. Cruz-Torres, M.E. Ruíz, J. Phys. Chem. A 106 (2002) 4645]. The explicit participation of the tunnel effect has been taken into account. The calculated rate coefficients provide a very good agreement with the experimental data. The best agreement for the overall alkane + OH reactions seemed to occur when the BHandHLYP geometries and partition functions are used. For propane and i-butane, in addition to the respective secondary and tertiary H-abstraction channels, the primary one has been considered. These pathways are confirmed to be significant in spite of the large differences in activation energies between primary and secondary or primary and tertiary channels, respectively of propane and i-butane reactions and should not be disregarded.     

Isopropylcyclopropane + OH gas phase reaction: a quantum chemistry + CVT/SCT approach

A theoretical study of the mechanism and kinetics of the OH hydrogen abstraction from isopropylcyclopropane (IPCP) is presented. Optimum geometries, frequencies and gradients have been computed at the BHandHLYP/6-311++G(d,p) level of theory for all stationary points, as well as for additional points along the minimum energy path (MEP). Energies have been improved by single-point calculations at the above geometries using CCSD(T)/6-311++G(d,p) to produce the potential energy surface. The rate coefficients are calculated for the temperature range 260-350 K by using canonical variational theory (CVT) with small-curvature tunneling (SCT) corrections. Our analysis suggests a stepwise mechanism involving the formation of a reactant complex in the entrance channel and a product complex in the exit channel, for all the modeled paths. The reactant complexes are examined in detail, because they exhibit alkene-like structure. The excellent agreement between the overall calculated and experimental rate coefficients at 298 K supports the reliability of the parameters obtained for the temperature dependence and branching ratios of the IPCP + OH reaction, proposed here for the fist time. The expression that best describes the studied reaction is k(overall) = 6.15 x 10(-13)e1747/RT cm3 x molecule(-1) x s(-1). The predicted activation energy is -0.89 kcal/mol.