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The effects of coarse-graining on the thermodynamic properties of molecular liquids are studied by computing the standard molar entropies of chloroform, 1,4-dioxane and neopentane using the two-pha...

The extremely large latent heat exchanged in phase transitions involving strong molecular orientational disordering has recently led to the proposal of plastic crystals as a feasible solution for solid-state barocaloric eco-friendly cooling technologies. Here we determine the reversible barocaloric response of four plastic crystals derived from neopentane [C(CH3)4]: (NH2)C(CH2OH)3 (TRIS for short), (NH2)(CH3) C(CH2OH)2 (AMP), (CH3)C(CH2OH)3 (PG) and (CH3)3C(CH2OH) (NPA). All of them display colossal entropy changes at their ordered-plastic phase transition, which is a primal requirement for competitive barocaloric materials. However, we show that it is also important to verify that the large barocaloric effects can be achieved using pressures that, while being moderate, are large enough to overcome the pressure-dependent hysteresis. From this quantity and using the quasi-direct method, we determine the minimum pressure needed to achieve reversible barocaloric effects, prev, for each compound. Specifically, we find a small and moderate prev for PG and NPA, respectively, which therefore display colossal reversible barocaloric effects comparable to harmful fluids used in current refrigerators and thus confirm the potential of plastic crystals as excellent alternatives. Instead, in TRIS and AMP, the obtained prev is excessive to yield reversible barocaloric effects useful for cyclic applications.

Chromium(VI) dialkyls are remarkably acidic, yielding a new set of anionic chromium alkylidenes upon deprotonation with KN(TMS)2. We describe the characterization of three anionic chromium alkylidenes of the type [(ArN)2Cr(=CHR)(CH2R]- (R = tBu, SiMe3, Ph; Ar = 2,6-diisopropylphenyl). NEt4[(ArN)2Cr(=CHSiMe3)(CH2SiMe3)] has been structurally characterized by X-ray diffraction. We have also studied the C-H activation of cyclohexane effected by the transient neopentylidene (ArN)2Cr(=CHCMe3). This reaction generated a tri-nuclear chromium(IV) complex, namely ‘[Cr(NAr)2]3’, as well as the two organic products cyclohexene and neopentane. A probable intermediate in this reaction could be trapped by PPh3 to form (ArN)2Cr(PPh3)2. The latter undergoes ligand substitution reactions with ethylene and CO to produce p-acid complexes of tetravalent chromium.

Palladium-containing catalyst based on binder-free granular sulfated zirconium oxide for n-butane isomerization has been investigated. It has been found that Pd content of 0.2–1.0 wt % slightly influences textural characteristics and other physicochemical properties of bifunctional catalysts; however, it determines their activity and selectivity in the reaction studied, with the optimal palladium content being 0.5 wt %. Parameters of the isomerization process have been studied depending on the composition of industrial n-butane fractions. It has been shown that impurities of isobutane, propane, neopentane, isopentane and pentane in an amount of no more than 2% do not exert a effect on isobutane production; nonetheless, the conversion of n-butane and selectivity for isobutane both increase when more pure n-butane fractions are used. It has been found that the process for isobutane production by isomerization of the n-butane fraction under the optimal conditions at H2 /n-C4 = 0.1 and 140–150°C makes it possible to obtain a high isobutane yield (up to 52 wt %) and avoid the undue formation of С1–С3 alkanes.

The understanding of major zeolite applications is partially based on diffusion of molecules inside or outside microporous networks. However, it is still a challenge to measure such phenomena. The diffusion ordered nuclear magnetic resonance spectroscopy (DOSY) technique has been reported to measure a probe molecule's diffusion inside porous solids. Pulsed-field gradient (PFG)-NMR has been used herein to measure the self-diffusivity of different probe molecules, such as neopentane, benzene, toluene and 1-dodecene with increasing dynamic diameter, respectively, on a series of H-ZSM-5 zeolites. The latter materials exhibit different crystal sizes, Si/Al ratios and the presence (or absence) of crystalline defects. In addition, shaped zeolite bodies representing industrial catalysts were compared with the afore-mentioned samples.

This work aims at the calculation of various inelastic cross sections for three pentane isomers, namely normal pentane, isopentane and neopentane. The direct ionisation, positronium formation, tota...

The GERG-2008 equation of state is the approved ISO standard (ISO 20765-2) for the calculation of thermophysical properties of natural gas mixtures. The composition of natural gas can vary considerably due to the diversity of origin. Further diversification was generated by adding hydrogen, biogas, or other non-conventional energy gases. In this work, high-precision experimental (p, ρ, T) data for two gravimetrically prepared synthetic natural gas mixtures are reported. One mixture resembled a conventional natural gas of 11 components (11 M) with a nominal mixture composition (amount-of-substance fraction) of 0.8845 for methane as the matrix compound with the other compounds being 0.005 for oxygen, 0.04 for nitrogen, 0.015 for carbon dioxide, 0.04 for ethane, 0.01 for propane, 0.002 each for n- and isobutane, and ultimately 0.0005 each for isopentane, n-pentane, and n-hexane. The other mixture was a 13-component hydrogen-enriched natural gas with a low calorific value featuring a nominal composition of 0.7885 for methane, 0.03 for hydrogen, 0.005 for helium, 0.12 for nitrogen, 0.04 for carbon dioxide, 0.0075 for ethane, 0.003 for propane, 0.002 each for n- and isobutane, and 0.0005 each for neopentane, isopentane, n-pentane, and n-hexane. Density measurements were performed in an isothermal operational mode at temperatures between 260 and 350 K and at pressures up to 20 MPa by using a single-sinker densimeter with magnetic suspension coupling. The data were compared with the corresponding densities calculated from both GERG-2008 and AGA8-DC92 equations of state to test their performance on real mixtures. The average absolute deviation from GERG-2008 (AGA8-DC92) is 0.027% (0.078%) for 11 M and 0.095% (0.062%) for the 13-component H2-enriched mixture, respectively. The corresponding maximum relative deviation from GERG-2008 (AGA8-DC92) amounts to 0.095% (0.127%) for 11 M and 0.291% (0.193%) for the H2-enriched mixture.

Effective and isotropic potentials of three hydrocarbon refrigerants were determined from an iterative inversion procedure, including ethylene (R1150), isobutane (R600a), and neopentane (R601b). By employing the inverted potentials, predictions of transport properties were performed with the aid of the kinetic theory of dilute gases. The viscosity coefficient, self-diffusion coefficient, and thermal diffusion factor of pure R1150, R600a, and R601b were presented over the temperature range from 273.15 K to 973.15 K at low density. Comparisons of the theoretically calculated values with the literature data were discussed. It is shown that the potentials obtained by the inversion scheme were able to predict accurate transport properties for these slightly polar ozone-safe hydrocarbon refrigerants.

Single-layer membranes of porous graphene, graphyne derivatives (α/α2/β-graphyne), and porous boron nitride (BN) with similar pore sizes (approximately 8 × 6 Å) have been evaluated for separating pentane isomers using first-principles calculations. In spite of their slightly bigger pore sizes, graphyne derivatives only allow linear pentane molecules to go through their native pores, while in contrast porous graphene and BN membranes only block dibranched isomers, i.e., neopentane molecules. Analyses of the geometric changes reveal that the structural flexibility of the membrane determines the penetration barrier. During the penetration of molecules, rigid membranes like graphyne derivatives may exhibit similar distortion to flexible porous graphene and BN; however the energy increase for the former is twice that for the latter. More importantly, the passing molecules experience about two times geometry distortion and four times energy barrier increase when going through rigid membranes compared with flexible membranes. The more deformed passing molecule and the less deformed rigid membrane can result in a much higher penetration barrier. Our results show that the flexibility of porous BN is comparable to that of porous graphene while graphyne derivatives are much more rigid.

Tetrakis(2-pyridylmethyleneimino)neopentane (L) was designed to form a spiro-structure after complex formation, where L plays a role of a double tetradentate bridging ligand. The X-ray diffraction study of [Cu2L(CF3SO3)4] clarified that the molecular structure was topologically spiro but the two coordination basal planes were not orthogonal with the dihedral angle of 49.8(1)°. The χmT value of [Cu2L(CF3SO3)4] showed a small increase on cooling below 10 K, indicating the presence of ferromagnetic coupling. Fitting to a singlet–triplet model gave 2J/kB = +0.293(7) K. The density-functional-theory calculation of the [Cu2L]4+ core reproduced the ferromagnetic coupling. Furthermore, from another calculation after removal of the neopentyl skeleton, through-bond interaction is clarified to be major in the exchange mechanism. The intervening sp3-hybridized carbon atoms may be spin-polarized.

The influence of the energy of low-voltage discharges in the liquid phase on the directions of fragmentation of toluene is studied. The discharges were generated by a 60 V DC source with a capacitor of 90 μF, 20090 μF, and 40090 μF. Fragmentation of toluene leads to the formation of carbon structures on the surface of graphite electrodes and in a liquid medium. It was revealed that an increase in the power of electric discharges leads to the growth of carbon structures on the surface of electrodes, reduces the output of the gas phase and finely dispersed carbon structures. The morphology and composition of solid phase products were determined by scanning electron microscopy and energy dispersive X-ray spectroscopy. Nanosized carbon structures are obtained in the form of aggregates - carbon nanohorns, which actively adsorb oxygen (content 0.9-3.6 at%). The composition of gaseous products was determined by gas chromatography. It was revealed that with an increase in the power of electric discharges, the hydrogen content slightly increases from 74.8 to 75.15 mol%, methane from 5.86 to 6.55 mol%, neopentane from 0.02 to 0.55 mol%. At the same time, the acetylene content in gaseous products decreases from 18.14 to 16.36 mol%.

We demonstrate by molecular dynamics simulation that co-non-solvency manifests itself in the solvent-induced interaction between three hydrophobes, methane, propane and neopentane, in methanol-water mixtures. Decomposition of the potential of mean force, based on the potential distribution theorem, clearly shows that the solute-solvent entropic change is responsible for stabilizing the aggregation of these hydrophobic molecules. Furthermore, we show that the entropic change pertains to the excluded volume effect.

This study explores the autoignition characteristics of three C5 isomers, namely n -pentane, 2-methylbutane ( iso -pentane) and 2,2-dimethylpropane ( neo -pentane). These measurements are intended to enhance understanding of C5 autoignition chemistry, and provide experimental data to guide improvements to a general hydrocarbon oxidation mechanism. To that end, the autoignition behavior of these three C5 isomers was investigated in a modified CFR engine at an intake temperature of 120 °C and a fixed engine speed of 600 rpm to determine the critical compression ratio (CCR) at which hot ignition occurs. To find the critical compression ratio, the engine compression ratio (CR) was gradually increased to the point where CO in the engine exhaust rapidly decreased and significant high temperature heat release was observed, while holding equivalence ratio constant. Fundamental ignition behaviors such as the CCR and the calculated percentage of low temperature heat release (%LTHR) demonstrate the impact of chain length and methyl substitutions on ignition reactivity. The %LTHR shows a stronger two stage heat release for n- pentane than for neo- pentane observed at critical ignition conditions. In contrast, single stage heat release is observed for iso- pentane, leading to the weakest overall oxidation reactivity of the three isomers. Key reaction paths forming conjugate alkenes and C 5 oxygenated species control the autoignition reactivity of n- pentane and iso- pentane within the low temperature and NTC regimes. However, neo- pentane forms no conjugate alkene due to its unique molecular structure, and instead produces iso -butene to retard its oxidation.

The effects of urea and taurine osmolytes on the hydrophobic interactions of methane and neopentane have been studied using molecular dynamics simulations. From the study of potential of mean force, it is observed that both urea and taurine enhance the association of methane and neopentane. The hydrophobic association of methane molecules is stabilized by entropy and destabilized by enthalpy in the mixtures of osmolytes at contact minima while the hydrophobic association of neopentane is stabilized by enthalpy and entropy. In these mixtures, hydrophobic solvation of methane molecules is enthalpy favorable and entropy unfavorable at SSM. The hydrophobic solvation of neopentane is stabilized by entropy and enthalpy. The study of radial distribution functions (RDFs), running coordination numbers, excess coordination numbers of water, urea and taurine molecules around hydrophobic molecules shows that methane shows salting-out (less soluble) and neopentane shows salting-in (more soluble) behavior in aqueous-urea. Methane and neopentane show salting-in behavior in aqueous-taurine solution because of preferential solvation by taurine. Salting-out behavior of methane has been observed in water-urea-taurine mixture. Neopentane shows salting-in behavior in aqueous solution of urea and taurine because of preferential binding with urea. These observations are supported by solvation free energies and spatial density maps.

The paper presents the results of studies on a mesoscopic self-assembling occurring in liquid state of hydrogen-bonded n-, sec-, and tert- butanols. In the first part of the paper it was revealed (basing on the literature data) that an unexpectedly high melting point of tert-butanol does not result from some extraordinary way of intermolecular clustering in that alcohol, but from an exceptional packing of its globular-like molecules. The conclusion arises from a similar behavior of neopentane – the non-polar analogue of tert-butanol. Our results of the static dielectric studies on butanol isomers, in particular the Kirkwood correlation factor and the orientation entropy increment show that the spatial arrangement of the hydrocarbon moiety surrounding –OH group, essentially determines the structure of emerging molecular clusters. The form of clusters are evolving from a chain-like in n-butanol to a great variety of branched entities (including the cyclic ones) in tert-butanol.

An ab initio quantum dynamics study has been performed to explore the distinct structural symmetry of C(CH3)4(+) in the ground electronic state compared to CH4(+). Additionally, the underlying details of the highly diffuse and complex vibronic structure of the first photoelectron band of C(CH3)4 have been investigated. Associated potential energy surfaces over the two-dimensional space of nuclear coordinates, subject to the T2⊗ (e + t2) Jahn-Teller effect, are established from extensive electronic structure calculations and (then) the nuclear dynamics calculations are done on them via wave packet propagation including the nonadiabatic coupling of the three electronic sheets. The theoretical results are in good agreement with experimental observations. The JT stabilization energies due to T2⊗e, T2⊗t2 and T2⊗ (e + t2) distortions in the X[combining tilde](2)T2 electronic manifold of C(CH3)4(+) illustrate that the highest stabilization occurs through the T2⊗t2-JT distortion (in the ground state of C(CH3)4(+)). However, CH4(+) gains such maximum stabilization due to T2⊗ (e + t2)-JT distortion. From this novel result and applying the epikernel principle, we propose that the structural evolution of C(CH3)4(+) from Td to C3v minimum energy configuration occurs via JT active vibrations of t2 symmetry, whereas CH4(+) rearranges to the C2v structure through a combination of JT active e and t2 bending vibrations.

Collisional energy transfer plays an important role in unimolecular reaction kinetics. This Letter presents classical trajectory calculations of the energy transfer processes in collisions between selected alkanes (ethane, propane, isobutane, and neopentane) and krypton at high temperature. The primary aim of this study was to elucidate the validity of the predicted energy transfer parameters by performing master equation analyses of their vibrational relaxation times and comparing the predicted values with the available experimental data. The results demonstrate the ability of classical trajectory calculations to accurately predict the parameters for vibrational energy transfer.

Using a static analytic method, experimental solubility data were obtained for tetra(5,5-dimethyl-1,3-dioxaphosphorinanyl-2-oxy) neopentane (DOPNP) in acetonitrile, acetone, methanol, ethanol, ethyl acetate, methyl acetate and methylethylketone at temperatures ranging from 293 to 333 K. Several commonly used thermodynamic models, including the ideal, modified Apelblat, Wilson, UNIQUAC and NRTL models, were applied to correlate the experimental solubility data. The binary interaction parameters of the above models were found to have a linear dependency on temperature and the coefficients were regressed. It can be seen that NRTL model is more suitable in describing the solubility data of DOPNP, compared with the other models. By using the van’t Hoff equation, the dissolution enthalpy, dissolution entropy, and Gibbs free energy change of DOPNP are predicted in different pure solvents.

Silica-supported Pd and shell/core PdAu nanoparticles of a similar size were evaluated for neopentane conversion. Monometallic Pd exhibited poor neopentane isomerization selectivity in favor of high selectivity to primary and secondary hydrogenolysis products. Similarly sized PdAu catalysts of increasing Pd weight loading were synthesized to evaluate the effect of increasing Pd monolayers on neopentane conversion. All PdAu catalysts had neopentane conversion selectivity within the range of monometallic Pd catalysts from previous work (~5–30%). However, there was an inverse relationship between Pd weight loading and neopentane isomerization selectivity. The increase in isomerization selectivity did not correlate to a decrease in heats of adsorption as seen with monometallic Pd catalysts, but was correlated with the catalyst surface structure which suggests a geometric effect as the cause for changes in catalytic performance rather than an electronic effect.

Binding of hydrocarbon guests to supramolecular hosts can lead to unusual geometric changes such as bending or coiling of guests upon encapsulation. Cucurbiturils (CBs) are classic cation binders that were recently used for the selective binding of small-membered hydrocarbons with a very high association constant (Ka ≈ 10(6) M(-1)). In this study, we have systematically investigated the binding of some alkanes to CB-[6] using a series of quantum chemical methods. The calculated binding free energies are very strong and are largely influenced by guest orientations inside the host and reorganization of host and guests. The computed (1)H NMR chemical shifts of the encapsulated alkanes agree with the experimental estimates thus confirming guest encapsulation. Further, we have shown that although binding of both cyclopentane and neopentane have very strong binding affinities (20 kcal mol(-1)), the selectivity of cyclopentane to neopentane at CB-[6] is a kinetically driven process through the computation of approximate transition state structures of both alkanes to CB-[6]. The calculated binding affinities with dispersion corrected density functionals (DFs) are very close to the experimental estimates, whereas DFs that lack dispersion correction predict that alkane binding to CB-[6] is largely unfavorable. Finally, we have investigated the binding of some long chain alkanes to several supramolecular hosts using dispersion corrected semiempirical methods which cannot be routinely studied through density functional theory methods due to the larger size of the system.

Aggregation processes in both the gas phase and aqueous solutions are analyzed by comparing aggregate size distributions obtained from molecular dynamics simulations with analytical predictions pertaining to a nonaggregating random mixture. The latter predictions are obtained by using the binomial distribution to predict the statistical properties of a uniformly mixed solution containing molecules of the same size and concentration as those in the solution of interest. Simulations are performed on systems containing neopentane dissolved in either methane, aqueous methanol, or aqueous NaI solutions. Comparisons of the theoretical and simulation results are used to both classify and quantify the influence of intermolecular interactions on such aggregation processes, including the equilibrium constants and thermodynamic functions pertaining to the partitioning of molecules between the bulk and first coordination shell of neopentane. Although the present results are primarily intended to describe and illustrate the random mixing analysis strategy, they also imply that neopentane has a greater tendency to aggregate with methane in the dense gas phase than with either methanol or iodide ions in aqueous solutions.

The "alkane branching effect" denotes the fact that simple alkanes with more highly branched carbon skeletons, for example, isobutane and neopentane, are more stable than their normal isomers, for example, n-butane and n-pentane. Although n-alkanes have no branches, the "kinks" (or "protobranches") in their chains (defined as the composite of 1,3-alkyl-alkyl interactions-including methine, methylene, and methyl groups as alkyl entities-present in most linear, cyclic, and branched alkanes, but not methane or ethane) also are associated with lower energies. Branching and protobranching stabilization energies are evaluated by isodesmic comparisons of protobranched alkanes with ethane. Accurate ab initio characterization of branching and protobranching stability requires post-self-consistent field (SCF) treatments, which account for medium range (∼1.5-3.0 Å) electron correlation. Localized molecular orbital second-order Møller-Plesset (LMO-MP2) partitioning of the correlation energies of simple alkanes into localized contributions indicates that correlation effects between electrons in 1,3-alkyl groups are largely responsible for the enhanced correlation energies and general stabilities of branched and protobranched alkanes.

The vibrational spectroscopy of C-H stretches in organic molecules is of considerable importance for the characterization of these systems and for exploration of their properties. These stretches are strongly anharmonic, and thus methods including anharmonicity have to be used. The vibrational self-consistent field (VSCF) is applied to the following organic compounds: acetone, dimethylacetylene, neopentane, toluene, ethylene, and cyclopropane. The computed spectra are compared to new experimental data, including Raman measurements of all molecules except cyclopropane and IR of acetone, neopentane, and ethylene. A high level of agreement is found for all of the molecules. The characteristic features of CH3 and CH2 groups are studied and analyzed in detail. A reliable, unambiguous assignment of vibrational modes to spectral peaks is provided. Several characteristic features of CH3 and CH2 vibrations in polyatomic molecules are clarified, providing easier assignments for different types of organic molecules.

Diffusion of pentane isomers in zeolites NaX has been investigated using pulsed field gradient nuclear magnetic resonance (PFG-NMR) and molecular dynamics (MD) techniques respectively. Temperature and concentration dependence of diffusivities have been studied. The diffusivities obtained from NMR are roughly an order of magnitude smaller than those obtained from MD. The dependence of diffusivity on loading at high temperatures exhibits a type I behavior according to the classification of Karger and Pfeifer [1] . NMR diffusivities of the isomers exhibit the order D ( n -pentane ) > D ( isopentane ) > D ( neopentane ) . The results from MD suggest that the diffusivities of the isomers follow the order D ( n -pentane ) D ( isopentane ) D ( neopentane ) . The activation energies from NMR show E a ( n -pentane ) E a ( isopentane ) E a ( neopentane ) whereas those from MD suggest the order E a ( n -pentane ) > E a ( isopentane ) > E a ( neopentane ) . The latter follows the predictions of levitation effect whereas those of NMR appears to be due to the presence of defects in the zeolite crystals. The differences between diffusivities estimated by NMR and MD are attributed to the longer time and length scales sampled by the NMR technique, as compared to MD.

The overall gas phase decomposition mechanism of tetraenopentyl zirconium precursor (Zr[CH2C(CH3)3]4) for the chemical vapor deposition of zirconium carbide thin films was investigated by using computational thermochemistry. Density functional theory (DFT) and harmonic vibrational frequency calculation were used to generate thermodynamic properties at each reaction step, based on which thermodynamic or kinetic preference of a reaction pathway was evaluated. While the preference of γ-hydrogen abstraction of neopentane over α-hydrogen abstraction was confirmed in the initial stage of ZrNp4 decomposition, they turned out to be competing instead of the dominant preference of γ-hydrogen abstraction. Methane formation at three subsequent reaction steps was explained by β-methyl migration, and the following α-hydrogen abstraction of methane based on the suggestion that α- and γ-hydrogen abstractions of neopentane are competing kinetically in previous reaction steps. Computational thermochemistry showed a possibility as a general tool to anticipate the gas phase decomposition mechanism of a precursor in chemical vapor deposition.

The isosteric enthalpy of adsorption for neopentane at relative pressures down to 3 × 10(-8) in MCM-41 was predicted for the temperature range from -15 to 0 °C. At such low pressures and temperatures, experimental measurements become problematic for this system. We used an atomistic model for MCM-41 obtained by means of a kinetic Monte Carlo method mimicking the synthesis of the material. The model was parametrized to represent experimental nitrogen adsorption isotherms at 77 K using grand canonical Monte Carlo simulations. The simulated isosteric enthalpy of adsorption shows very good agreement with available experimental data, demonstrating that GCMC simulations can predict heats of adsorption for conditions that are challenging for experimental measurements. Additional insights into the adsorption mechanisms, derived from energetic analysis at the molecular level, are also presented.

Intermolecular interactions and parameters for use in MD studies of large molecule systems have earlier been determined for hydrocarbons, carbon tetrahalides and sulfur. The paper reports a model representing nonbonding interactions between silane molecules, which were examined in the same way as hydrocarbons in an earlier (neopentane, isopropane, propane, and ethane) study. Intermolecular potentials were determined for 11 combinations of silane compound pairs (silane SiH4, disilane Si2H6, trisilane Si3H8, isotetrasilane Si4H10 and neopentasilane Si5H12) with MP2/aug(df)-6-311G∗ ab initio calculations. The most stable dimer configurations were identified. With use of the modified Morse potential model to represent the interactions, 276 new potential energy surfaces were generated for silane dimers. Separate and generic pair potentials were calculated for the silanes. The pair potentials can be used in MD studies of silanes.

The effects of initial water content on steam reforming of aliphatic hydrocarbons such as methane, propane, and neopentane with nonthermal plasma were analyzed in terms of substrate conversion, carbon recovery, and product selectivity. It was found that water addition increased CO2 yield despite a decrease in substrate conversion. The number of carbon atoms in the substrate hydrocarbon affected the additive effect due to the insufficient supply of oxygen atoms from water. Plausible reaction pathways for the conversion of substrate to COx are proposed to explain the relative concentrations of COx species; these pathways involved different precursors for CO and CO2.

The effect of electrostatic interactions on the absorption of the positively charged reversible inhibitor tetramethylammonium, its neutral structural analogue neopentane C(CH(3))(4), and the natural substrate acethylcholine to the active sites of acetylcholinesterase and butyrylcholinesterase has been studied by molecular modeling methods. It has been shown that the dominant absorption of positively charged ligands is due to the anchoring of the cationic group of the ligand in the anionic subsite of both enzymes through the interaction of the pi-cation with the benzene ring of tryptophan. The correlation between the free energy of complex formation and the catalytic activity of charged tetramethylammonium has been revealed for both enzymes. It has been shown that the effective binding of the acetylcholine molecule requires the additional activation of the enzyme.

The adsorption properties of carbon tetrachloride, neopentane, and cyclohexane in MCM-41 with heterogeneous and cylindrical pores have been studied by using grand canonical ensemble Monte Carlo simulation. The adsorption isotherm, average potential of adsorbate, isosteric heat of adsorption, and number density of molecules in MCM-41 were calculated. The simulated isotherms were compared with experimental ones. Also, different adsorption behaviors in MCM-41 with pore diameter of 2.2 and 3.2 nm were discussed. The capillary-condensation pressure increased for a given adsorbate with an increase in pore diameter. The average densities of carbon tetrachloride, neopentane, and cyclohexane in the two different pores above the capillary-condensation pressure were smaller than the corresponding liquid densities by about 12%. The adsorbate molecules did not form the multilayer in pore below the capillary-condensation pressure. The number of adsorption layers of molecules was constant in a given pore for the three adsorbates above the capillary-condensation pressure. Carbon tetrachloride molecules in pore were also ordered along the pore axis.

Tetrafluoromethane, CF 4 , is markedly less soluble in water than methane and neopentane around room temperature: it is a superhydrophobic solute. An analysis of the physical origin of this superhydrophobicity is performed, exploiting literature thermodynamic data covering the 5–55 °C temperature range. It results that the CF 4 –water dispersion interactions are markedly weaker in magnitude than those of a ‘hypothetical’ hydrocarbon having the same size of tetrafluoromethane, providing a smaller counterbalancing effect of the work spent to create the cavity in water. The weakness of the CF 4 –water dispersion interactions is due to the very small polarizability of CF 4 , which, in turn, is caused by the strong electronegativity of fluorine atoms.

The grafting of tetraneopentylchromium(IV) onto the surface hydroxyls of silica has been investigated by varying both the method of deposition and the nature of the silica support. Reaction of the volatile organometallic with the silica surface in vacuo is compared with reaction in solution. A faster reaction but a lower ultimate Cr loading was obtained using the solution deposition technique. The reactions of the organometallic compound with Aerosil 200, a fumed silica often used to model catalyst supports, and Sylopol 952, a silica gel used as a carrier for chromium-based ethylene polymerization catalysts, are compared. After thermal pretreatment at 200 °C, grafting on both supports yields bis(neopentyl)chromium(IV) fragments regardless of the grafting method used, suggesting that a paired arrangement of the surface hydroxyl groups exists on both types of silicas. The higher Cr loading achieved on the silica gel is attributed to its higher surface area. Thermally-induced neopentane elimination from the grafted bis(neopentyl)chromium(IV) fragments occurs at the same rate and with the same stoichiometry for both Aerosil- and Sylopol-supported materials. Consequently, interactions of the grafted organometallic fragments with nearby siloxanes appear to be unimportant in the early stages of the transformation of bis(alkyl)chromium(IV) to the alkylidene.

The thermodynamic adsorption characteristics of tetramethylsilane (TMS) molecules on graphitized carbon black (GCB) were for the first time determined experimentally and by molecular statistics methods. The potential function parameters of pair molecular interactions (φ(r)) between Si and C atoms on the basal face of graphite were calculated in the atom-atom approximation of the semiempirical molecular-statistical theory of adsorption. The contributions of Si and C atoms to thermodynamic adsorption characteristics are compared for the example of nonspecific adsorption of TMS and isostructural neopentane molecules on the flat surface of GCB.

The isotropic (n-6) Lennard-Jones temperature-dependent potential (LJTDP) together with the Hohm−Zarkova−Damyanova mixing rules is used to predict second interaction pVT virial coefficients BAB(T),...

The interactions between an oxidic support and Pt particles were explored in a series of platinum catalysts supported on amorphous silica–alumina used for the hydrogenation of tetralin and the hydrogenolysis of neopentane. The activity of the nanosized Pt particles increased with increasing intermediate electronegativity of the support for all supports with accessible Lewis acid sites. A compensation effect between the preexponential factor and the apparent energy of activation was observed for both reactions, attributed to the stronger adsorption of the reactants and intermediates on Pt induced by the increasingly electronegative supports. The product distribution in tetralin hydrogenation also points to stronger adsorption on Pt with increasing intermediate electronegativity of the support. X-ray absorption near-edge structure (XANES) findings indicate that the stronger interaction of the reactants is related to a reduced electron density on the platinum particles.