Assessment of performance of the general purpose polarizable force field QMPFF3 in condensed phase

The recently introduced force field (FF) QMPFF3 is thoroughly validated in gas, liquid, and solid phases. For the first time, it is demonstrated that a physically well-grounded general purpose FF fitted exclusively to a comprehensive set of high level vacuum quantum mechanical data applied as it is to simulation of condensed phase provides high transferability for a wide range of chemical compounds. QMPFF3 demonstrates accuracy comparable with that of the FFs explicitly fitted to condensed phase data, but due to high transferability it is expected to be successful in simulating large molecular complexes.     

Anisotropic nonadditive ab initio force field for noncovalent interactions of H2

A quantum mechanical polarizable force field (QMPFF) has been applied to the noncovalent interactions of molecular hydrogen as well as closed-shell monoatomic species (CSMS): rare gases, alkali cations, and halide anions. The importance of all the main energy components is demonstrated: electrostatics (including penetration effect), exchange repulsion, dispersion, and induction. As the MP2 level of quantum mechanics, which is used to parametrize QMPFF, significantly underestimates the H2-H2 dimer binding energy, the force field was refined using state-of-the-art CCSD(T) data. The approach demonstrates excellent transferability, which is confirmed by accurate reproduction of mixed H2-CSMS dimers and the second virial coefficient of hydrogen vapor.     

Prediction of cyclohexane-water distribution coefficient for SAMPL5 drug-like compounds with the QMPFF3 and ARROW polarizable force fields

We present the performance of blind predictions of water—cyclohexane distribution coefficients for 53 drug-like compounds in the SAMPL5 challenge by three methods currently in use within our group. Two of them utilize QMPFF3 and ARROW, polarizable force-fields of varying complexity, and the third uses the General Amber Force-Field (GAFF). The polarizable FF’s are implemented in an in-house MD package, Arbalest. We find that when we had time to parametrize the functional groups with care (batch 0), the polarizable force-fields outperformed the non-polarizable one. Conversely, on the full set of 53 compounds, GAFF performed better than both QMPFF3 and ARROW. We also describe the torsion-restrain method we used to improve sampling of molecular conformational space and thus the overall accuracy of prediction. The SAMPL5 challenge highlighted several drawbacks of our force-fields, such as our significant systematic over-estimation of hydrophobic interactions, specifically for alkanes and aromatic rings.     

Excess gibbs energies for the benzene + n-hexadecane system at 298.15 and 323.15 K

The vapor pressure of the system benzene +n-hexadecane is measured by means of a static apparatus. Excess Gibbs energies are calculated using a modified Barker's method, and fitted to an equation proposed by Marsh. The regression analysis is based on the principle of maximum likelihood. The selection of the best set of estimates of the parameters is also discussed. The results obtained in this work are compared with those reported by other authors for the same system. Due to the lack of heat capacity data for this system, an approximation to calculate temperature dependence is studied.     

Quantum-Chemical Study of Methyl Phenyl Sulfide

Steric and electronic structure of the methyl phenyl sulfide molecule was studied by nonempirical quantum-chemical methods. The calculations were performed by the B3LYP and MP2 procedures with account taken of electronic correlation using extended 6-311++G(3d,p) basis sets. The use of a balanced method and basis set allowed us to avoid discrepancy between the experimental and calculated data reported by other authors. The results confirmed coplanar orientation of the CÄSÄC fragment and the benzene ring, which follows from most experimental studies.     

Isobaric vapor–liquid equilibrium of systems containing triethyl orthoformate at 101.3 kPa

Isobaric vapor–liquid equilibrium data of ethanol(1)-triethyl orthoformate(2), benzene(1)-triethyl orthoformate(2) and ethanol(1)-benzene(2)-triethyl orthoformate(3) were measured at 101.3 kPa and under a wide range of temperatures (349–420 K), using the Rose–Williams still modified by the authors. The experimental data of binary systems were tested for thermodynamic consistency with the method of Fredenslund and coworkers and correlated satisfactorily with SRK equation and PR equation of state. The VLE data of ethanol(1)-benzene(2)-triethyl orthoformate(3) ternary system were tested with the method of McDermont–Ellis and were predicted with the parameters of SRK and PR equation of state obtained from binary systems.     

Excess magnitudes for the benzene + n-dodecane system at 298.15 and 323.15 K

The vapor pressures for benzene + n-dodecane mixtures have been measured using a static apparatus. Values for the excess Gibbs energy have been calculated using a modified form of Barker's method and fitted to a Padé approximant equation. Selection of the most adequate approximant is made according to objective criteria. The results are compared with those corresponding to other benzene + n-alkane systems. The values for the activity coefficient of benzene at infinite dilution calculated from these data agrees very well with the values obtained by gas-liquid chromatography.     

Estimation of pore size distribution in MCM-41-type silica using a simple desorption technique

A recently developed dynamic desorption technique is used for obtaining vapor isotherms on porous materials. This gravimetric technique does not require any preliminary calibration and is based on analyzing the kinetics of liquid evaporation from a porous sample under quasi-steady state conditions. The crucial feature of the technique is concerned with the fact that no vapor pressure measurements are necessary. The technique is illustrated by desorption of benzene vapors from mesoporous silica MCM-41. To calculate the pore size distribution, the Derjaguin–Broekhoff–de Boer theory in its combination with the Wheeler model for capillary condensation is used. In the calculations, the reference data on benzene adsorption on a nonporous silica gel from two different sources (published by different authors) are applied. The mean mesopore sizes estimated from desorption isotherms are shown to be in a fair agreement with the calculations through the geometrical method based on the X-ray diffraction data. The dynamic desorption technique can serve as an additional tool for the characterization of a porous media.     

Electrochemistry of polyaminobenzenes: Part 2. Oxidation of hexakis(dimethylamino)benzene at high potentials

Hexakis(dimethylamino)benzene is electrochemically oxidized to species with oxidation states higher than that of a tetracation. The reaction is followed by cyclic voltammetry. A mechanistic scheme of the electrode reaction mechanism is proposed. Computer simulations of cyclic voltammograms at scan rates between 0.02 and 50 V s⁻¹ allow the estimation of reaction parameters. A comparison of the potentials for the redox steps with data by other authors supports a re-interpretation of their results.     

A physicochemical study of binary mixtures of commercial solvent extractant,Alamine 308, with benzene at 303.15 K

An acoustic study of the binary Alamine 308 (triisooctylamine)-benzene system was performed by measuring ultrasonic velocity, viscosity and density. Interactions in the liquid mixture were explained on the basis of excess non-linearity parameters and other relevant data, such as the degree of molecular interaction, molar sound velocity, etc. In addition, the experimental velocities were compared with theoretical estimates using various empirical relations, and the relative merits of the corresponding theories and relations were discussed in terms of percentage variations. The basic aim of this work was to assess the type of solute-solvent interaction between a nonpolar extractant (Alamine 308) and a nonpolar diluent (benzene). The text was submitted by the authors in English.     

In situ sum frequency generation vibrational spectroscopy observation of a reactive surface intermediate during high-pressure benzene hydrogenation

Sum frequency generation surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to identify a reactive surface intermediate in situ during hydrogenation of benzene on a Pt(111) single crystal surface at Torr pressures. Upon adsorption at 310 K, both chemisorbed and physisorbed benzene coexist on the surface, a result which has not previously been observed. Kinetic measurements show a linear compensation effect for the production of both cyclohexane and cyclohexene. From these data the isokinetic temperature was identified and correlated to the chemisorbed benzene species, which were probed by means of vibrational spectroscopy. Additionally, chemisorbed benzene was determined to be a reactive intermediate, which is critical for hydrogenation.     

Monitoring of trace levels of p-dioxan in high purity benzene feedstock by capillary gas chromatography

Summary A procedure has been standarized for the determination of p-dioxan (1,4-dioxan) in benzene feedstock in the range of 1 to 100 ppm by capillary GC. The GC conditions such as oven temperature, length of the column etc were optimized to achieve better resolution of p-dioxan from hydrocarbons. The standard addition method of quantitation, was used to determine the amount of p-dioxan and was found to give better results than those obtained by external standardization. Prior to analysis the identity of the p-dioxan peak was established by GC-MS. The proposed method has been applied for the monitoring of p-dioxan in high purity benzene feedstock produced by the Udex extraction process in the refinery. The data were used for optimization of plant conditions for the production of high purity benzene feedstock. By using this method, the p-dioxan content down to 0.5 ppm can be determined in the benzene feedstock.     

Vapor-liquid equilibria forn-tetradecane-benzene mixtures at 25 and 50°C

Vapor pressures for the benzene+n-tetradecane system have been measured using a static apparatus. The excess Gibbs free energy was calculated using a modified Barker method and a Pade approximant equation. The selection of the most adequate approximation is discussed. Results are compared with those corresponding to other thermodynamic properties. The activity coefficient of benzene at infinite dilution calculated from these data agrees well with the value obtained from the literature.     

TBP-TTA-C6H6三元体系活度系数的研究

如何计算与测量多组元体系的活度系数,是一个重要问题。我们的工作是选取了磷酸三丁酯(TBP)与硫国酰基三氟丙酮(TTA)溶于苯的体系,进行了实验测量与理论计算,理论与实验取得了基本一致的结果。     

Adsorption, structure and dynamics of benzene in ordered and disordered porous carbons

Molecular simulations are used to study the adsorption, structure, and dynamics of benzene at 298 K in atomistic models of ordered and disordered nanoporous carbons. The ordered porous carbon is a regular slit pore made up of graphene sheets. The disordered porous carbon is a structural model that reproduces the morphological (pore shape) and topological (pore connectivity) disorder of saccharose-based porous carbons. As expected for pores of a regular geometry, the filling occurs at well-defined pressures which are an increasing function of the pore width H. In contrast, in qualitative agreement with experimental data for activated carbon fibers, the filling of the disordered carbon is continuous and spans over a large pressure range. The structure and dynamics of benzene in the disordered carbon also strongly depart from that for the slit pore geometry. While benzene in the slit graphite nanopores exhibits significant layering, benzene in the disordered porous carbon exhibits a liquid-like structure very close to its bulk counterpart. Both the ordering and self-diffusivity of benzene in the graphite nanopores depend in a complex manner on the pore width. The dynamics is either slower or faster than its bulk counterpart; our data show that the self-diffusivity decreases as the number of confined layers n divided by the pore width H increases (except for very small pore sizes for which benzene crystallizes and is necessarily slower than the liquid phase). The dynamics of benzene in the disordered porous carbon is isotropic and is much slower than that for the graphite slit nanopores (even with the smallest slit nanopore considered in this work). The results above show that the adsorption, structure, and dynamics of benzene confined in disordered porous carbons cannot be described in simple terms using an ideal model such as the slit pore geometry.     

Sigma and pi contributions to the induced magnetic field: indicators for the mobility of electrons in molecules

The authors discuss the role of the sigma and pi contributions to the induced magnetic field for simple hydrocarbons containing a double or a triple bond, as well as for benzene and cyclobutadiene. While the magnetic field induced by the sigma electrons is short-ranged, the pi system is responsible for the formation of long-range cones. These cones influence the chemical shift of atoms by additional shielding (for aromatic) or deshielding (for antiaromatic molecules) contributions. While the hydrogen atoms of benzene are found to lie within the deshielded region of the magnetic field induced by the pi electrons, they are shielded by the total induced magnetic field. The induced magnetic field of the pi electrons support Pople's model on the basis of first-principles calculations.     

Phase Equilibria in the Systems Ethyl 1,1-Dimethylethyl Ether + Benzene + 2,2,4-Trimethylpentane and Benzene + 2,2,4-Trimethylpentane at 94.00 kPa

Abstract

Consistent vapor-liquid equilibria data at 94.00 kPa have been determined for the ternary system ethyl 1,1-dimethylethyl ether + benzene + 2,2,4-trimethylpentane and for its constituent binary benzene + 2,2,4-trimethylpentane, in the temperature range 343 to 370 K. The systems exhibit slight positive deviations from ideal behavior and the system benzene + 2,2,4-trimethylpentane presents an azeotrope. The VLE data have been correlated with the mole fraction using the Redlich-Kister, Wilson, NRTL, UNIQUAC, and Tamir relations. These models, in addition to UNIFAC, allow good prediction of the VLE properties of the ternary system from those of the pertinent binary systems.     

Theoretical studies on tunneling ionizations from the doubly degenerate highest occupied molecular orbitals of benzene in intense laser fields

Combining our generalized Keldysh theory [Sov. Phys. JETP 20, 1307 (1965)] with the molecular orbital theory, the authors theoretically study tunneling ionizations of neutral benzene in intense linearly polarized Ti:sapphire laser fields (800 nm). They consider the ionizations from the highest occupied molecular orbitals (HOMOs) of the ground electronic state. The double degeneracy of the HOMOs is properly taken into account. In the theory, molecular ionizations consist of the individual ionizations from each atom and the quantum interferences between them. The theory reproduces the experimental data well. The authors also show that the polarization dependence of the ionization rates is strongly influenced by the quantum interferences.