Intrinsic Gas-phase Research Articles

Modeling gas flow in low-permeability formations: An efficient combination of mixed finite elements and high order time integration schemes

Numerical simulation of gas flow in low permeability formations is a challenging task due to the high nonlinearity induced by (i) the compressibility of the gas, (ii) the Klinkenberg slippage effect and (iii) the Langmuir adsorption of the gas on the pore surface. Because of these nonlinearities, modeling gas flow in low permeability formations requires a great deal of computational effort. In this work, we develop an efficient numerical model using advanced spatial and temporal discretization methods for a simultaneous solution of the coupled equations of gas flow, cubic Peng-Robinson equation of state, slippage effect and Langmuir adsorption. The spatial discretization is performed with the lumped hybrid formulation of the mixed finite element method which is well adapted for fluid flow in heterogeneous porous media. The time integration is performed with high-order methods via the method of lines (MOL) which allows large time steps and efficient solution of the nonlinear system of equations. Numerical experiments, performed for gas extraction in a heterogeneous domain, point out the high efficiency of the new model since it can be until 10 times more efficient than the classical first-order time discretization method. Results of global sensitivity analysis show that the intrinsic gas-phase permeability and the Klinkenberg factor are the most influential parameters controlling the pumping rate in the case of gas extraction in a homogeneous domain.

Gas-phase F-atom migration reaction of deprotonated N-fluoroarenesulfonamides.

Recently N-Fluoroarenesulfonamides (ArSO2 NHF) were found to be promising precursors for the preparation of N-fluorobenzenesulfonimide derivatives without applying F2 . However, very few studies have discussed the mass spectrometric behaviors of ArSO2 NHF with N-F structure. In this article, we applied high-resolution electrospray ionization tandem mass spectrometry (HR-ESI-MS/MS) to study the effect on the mass spectrometric behaviors of ArSO2 NHF after the introduction of the F-atom to the N-atom of ArSO2 NH2 . High-resolution electrospray ionization mass spectrometry (HR-ESI-MS) experiments showed that ArSO2 NHF produced only good signals in negative ion mode, and the dominating product ion SO2 F- at m/z 83 was observed in all HR-ESI-MS/MS of ArSO2 NF- with different substituents in the Ar group. The formation of the product ion SO2 F- was proof of the gas-phase F-atom migration rearrangement from the N-atom to the S-atom in ESI-MS/MS of ArSO2 NF- . To fully explain the gas-phase reaction mechanism from ArSO2 NF- to SO2 F- , we studied the HR-ESI-MS/MS of deprotonated ArSO2 NHF and also performed theoretical calculations. Both results confirmed that ArSO2 NF- first underwent Smiles rearrangement to yield intermediate I (INT1) ArNFSO2 - , and then the F-atom of ArNFSO2 - migrated from the N-atom to the S-atom to form intermediate II (INT2) ArN- SO2 F, which finally dissociated to SO2 F- at m/z 83 with loss of a neutral nitrene (ArN). All these results showed that the formation of the product ion SO2 F- from ArSO2 NF- was a common and intrinsic gas-phase reactivity of ArSO2 NF- .

Electrolyte Reactivity on the MgV2O4 Cathode Surface.

Predictive understanding of the molecular interaction of electrolyte ions and solvent molecules and their chemical reactivity on electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at the electrode-electrolyte interface of multivalent magnesium batteries. In this work, the isolated intrinsic reactivities of prominent chemical species present in magnesium bis(trifluoromethanesulfonimide) (Mg(TFSI)2) in diglyme (G2) electrolytes, including ionic (TFSI-, [Mg(TFSI)]+, [Mg(TFSI):G2]+, and [Mg(TFSI):2G2]+) as well as neutral molecules (G2) on a well-defined magnesium vanadate cathode (MgV2O4) surface, have been studied using a combination of first-principles calculations and multimodal spectroscopy analysis. Our calculations show that nonsolvated [Mg(TFSI)]+ is the strongest adsorbing species on the MgV2O4 surface compared with all other ions while partially solvated [Mg(TFSI):G2]+ is the most reactive species. The cleavage of C-S bonds in TFSI- to form CF3- is predicted to be the most desired pathway for all ionic species, which is followed by the cleavage of C-O bonds of G2 to yield CH3+ or OCH3- species. The strong stabilization and electron transfer between ionic electrolyte species and MgV2O4 is found to significantly favor these decomposition reactions on the surface compared with intrinsic gas-phase dissociation. Experimentally, we used state-of-the-art ion soft landing to selectively deposit mass-selected TFSI-, [Mg(TFSI):G2]+, and [Mg(TFSI):2G2]+ on a MgV2O4 thin film to form a well-defined electrolyte-MgV2O4 interface. Analysis of the soft-landed interface using X-ray photoelectron, X-ray absorption near-edge structure, electron energy-loss spectroscopies, as well as transmission electron microscopy confirmed the presence of decomposition species (e.g., MgFx, carbonates) and the higher amount of MgFx with [Mg(TFSI):G2]+ formed in the interfacial region, which corroborates the theoretical observation. Overall, these results indicate that Mg2+ desolvation results in electrolyte decomposition facilitated by surface adsorption, charge transfer, and the formation of passivating fluorides on the MgV2O4 cathode surface. This work provides the first evidence of the primary mechanisms leading to electrolyte decomposition at high-voltage oxide surfaces in multivalent batteries and suggests that the design of new, anodically stable electrolytes must target systems that facilitate cation desolvation.

The resolved chemical abundance properties within the interstellar medium of star-forming galaxies at z≈ 1.5

ABSTRACT We exploit the unprecedented depth of integral field data from the KMOS Ultra-deep Rotational Velocity Survey (KURVS) to analyse the strong (Hα) and forbidden ([N ii], [S ii]) emission line ratios in 22 main-sequence galaxies at $z\, \approx \, 1.5$. Using the [N ii]/Hα emission-line ratio, we confirm the presence of the stellar mass – gas-phase metallicity relation at this epoch, with galaxies exhibiting on average 0.13 ± 0.04 dex lower gas-phase metallicity (12 + log(O/H)M13 = 8.40 ± 0.03) for a given stellar mass (log10(M*[M⊙] = 10.1 ± 0.1) .than local main-sequence galaxies. We determine the galaxy-integrated [S ii] doublet ratio, with a median value of [S ii]λ6716/λ6731 = 1.26 ± 0.14 equivalent to an electron density of log10(ne[cm−3]) = 1.95 ± 0.12. Utilising CANDELS HST multi-band imaging we define the pixel surface-mass and star-formation rate density in each galaxy and spatially resolve the fundamental metallicity relation at $z\, \approx \, 1.5$, finding an evolution of 0.05 ± 0.01 dex compared to the local relation. We quantify the intrinsic gas-phase metallicity gradient within the galaxies using the [N ii]/Hα calibration, finding a median annuli-based gradient of ΔZ/ΔR = −0.015 ± 0.005 dex kpc−1. Finally, we examine the azimuthal variations in gas-phase metallicity, which show a negative correlation with the galaxy integrated star-formation rate surface density ($r_{\rm s}\,$ = −0.40, ps = 0.07) but no connection to the galaxies kinematic or morphological properties nor radial variations in stellar mass surface density or star formation rate surface density. This suggests both the radial and azimuthal variations in interstellar medium properties are connected to the galaxy integrated density of recent star formation.

Turbulence Regulates the Rate of Planetesimal Formation via Gravitational Collapse

Abstract We study how the interaction between the streaming instability (SI) and intrinsic gas-phase turbulence affects planetesimal formation via gravitational collapse in protoplanetary disks. Turbulence impedes the formation of particle clumps by acting as an effective turbulent diffusivity, but it can also promote planetesimal formation by concentrating solids, for example, in zonal flows. We quantify the effect of turbulent diffusivity using numerical simulations of the SI in small local domains, forced with velocity perturbations that establish approximately Kolmogorov-like turbulence. We find that planetesimal formation is suppressed by turbulence once velocity fluctuations exceed ≃ (10−3.5–10−3) . Turbulence whose strength is just below the threshold reduces the rate at which solids are bound into clumps. Our results suggest that the well-established turbulent thickening of the midplane solid layer is the primary mechanism by which turbulence influences planetesimal formation and that planetesimal formation requires a midplane solid-to-gas ratio ϵ ≳ 0.5. We also quantify the initial planetesimal mass function using a new clump-tracking method to determine each planetesimal mass shortly after collapse. For models in which planetesimals form, we show that the mass function is well described by a broken power law, whose parameters are robust to the inclusion and strength of imposed turbulence. Turbulence in protoplanetary disks is likely to substantially exceed the threshold for planetesimal formation at radii where temperatures T ≳ 103 K lead to thermal ionization. Planetesimal formation may therefore be unviable in the inner disk out to 2–3 times the dust sublimation radius.

Gas-Phase Protonation Thermodynamics of Biological Lipids: Experiment, Theory, and Implications.

Phospholipids are important to cellular function and are a vital structural component of plasma and organelle membranes. These membranes isolate the cell from its environment, allow regulation of the internal concentrations of ions and small molecules, and host diverse types of membrane proteins. It remains extremely challenging to identify specific membrane protein-lipid interactions and their relative strengths. Native mass spectrometry, an intrinsically gas-phase method, has recently been demonstrated as a promising tool for identifying endogenous protein-lipid interactions. However, to what extent the identified interactions reflect solution- versus gas-phase binding strengths is not known. Here, the "Extended" Kinetic Method and ab initio computations at three different levels of theory are used to experimentally and theoretically determine intrinsic gas-phase basicities (GB, ΔG for deprotonation of the protonated base) and proton affinities (PA, ΔH for deprotonation of the protonated base) of six lipids representing common phospholipid types. Gas-phase acidities (ΔG and ΔH for deprotonation) of neutral phospholipids are also evaluated computationally and ranked experimentally. Intriguingly, it is found that two of these phospholipids, sphingomyelin and phosphatidylcholine, have the highest GB of any small, monomeric biomolecules measured to date and are more basic than arginine. Phosphatidylethanolamine and phosphatidylserine are found to be similar in GB to basic amino acids lysine and histidine, and phosphatidic acid and phosphatidylglycerol are the least basic of the six lipid types studied, though still more basic than alanine. Kinetic Method experiments and theory show that the gas-phase acidities of these phospholipids are high but less extreme than their GB values, with phosphatidylserine and phosphatidylglycerol being the most acidic. These results indicate that sphingomyelin and phosphatidylcholine lipids can act as charge-reducing agents when dissociated from native membrane protein-lipid complexes in the gas phase and provide a straightforward model to explain the results of several recent native mass spectrometry studies of protein-lipid complexes.

Reaction of ionised steryl esters with ozone in the gas phase.

Cholesterol is an ubiquitous membrane lipid, that also serves as a precursor to many steroid hormones. The 5,6 carbon-carbon double bond on the tetracyclic carbon backbone of cholesterol is an attractive target for ozone with the reaction giving rise to a wide range of possibly bioactive molecules. Despite this, little is known about the ozonolysis of cholesterol esters, which often possess an additional double bond(s) on the fatty acyl chain. Understanding the intrinsic gas phase reaction of ozone with the two disparate double bond positions on cholesteryl esters can inform our understanding of these processes in vivo, particularly reactions occurring at the air-water interface (e.g., tear film lipid layer) and on the surfaces of the body where these cholesterol and cholesteryl esters may be present (e.g., sebum). In the present work we describe the gas phase ozonolysis of lithium and sodium cations formed from three steryl esters: two isomeric for double bond position (cholestanyl oleate and cholesteryl stearate), and a third with carbon-carbon double bonds present in both the sterol ring system and fatty acyl chain (cholesteryl oleate). We confirm the enhanced reactivity of the endocyclic carbon-carbon double bond with ozone over double bonds present in the acyl chain, and elucidate competitive interactions between the two double bond positions during ozonolysis. Elucidation of the mechanisms underlying this interaction is important for both understanding these processes in vivo and for deploying ozonolysis chemistry in analytical strategies for lipidomics.

Superacidity of P(OH)3 and SO(OH)2 derivatives of cyclopentadiene and vinylcyclopentadiene in the gas phase: A computational DFT analysis

Strong Brønsted acids were designed using a simple strategy of replacing double-bonded oxygen atoms in mineral acids H3PO4 and H2SO4 with cyclopentadiene and vinylcyclopentadiene moieties, followed by a substitution with strong electron-withdrawing cyano groups. Their intrinsic gas-phase acidity was assessed by the B3LYP density functional theory calculations employing the 6-311++G(d,p) basis set, and many highly potent superacids were identified. The pronounced acidity of these conjugates is due to two predominant factors, namely, (i) an increase in the aromaticity of the five-membered ring on deprotonation, as evaluated through the NICS parameters, and (ii) an extension of the conjugated π-network enabled by the cyano groups that efficiently distribute an excess negative charge over a large number of atoms in conjugate bases. The SO(OH)2 derivatives are generally more acidic than the corresponding P(OH)3 counterparts so that the ΔHacid values for the SO(OH)2 and P(OH)3 derivatives with CN substituents evaluated here are 260-266 and 263-272 kcal mol−1, respectively. Given the growing interest in highly acidic molecules together with related acidic catalysts and metal complexing agents, the results presented here should direct the attention toward utilizing proposed systems as improved organic materials, and their synthesis is highly recommended.

How difficult are anion-molecule SNAr reactions of unactivated arenes in the gas phase, dimethyl sulfoxide, and methanol solvents?

Nucleophilic substitution on the aromatic ring (SNAr) is a very important reaction for organic transformations. This kind of reaction is usually difficult to take place, requiring organometallic catalysis or activation of the ring by electron withdrawing groups to turn the nucleophilic attack possible. In this work, the relative importance of intrinsic gas phase barrier and the solvent effect on several SNAr reactions using theoretical calculations were investigated. The reactions of the anions OH−, CN−, and CH3O− and the enolates CH3COCH2− and CH3COCHCOCH3− with bromobenzene and (o, m, p)-methoxy bromobenzene in methanol and dimethyl sulfoxide as solvents were considered. The OH− and CH3O− ions are highly reactive in the gas phase. However, the solvent effect induces a high activation barrier in solution, turning the reaction difficult, although feasible. The CN− and CH3COCHCOCH3− ions have high activation barriers even in the gas phase. The interesting CH3COCH2− ion has a moderate barrier in the gas phase, although the free energy barrier in DMSO solution reaches 33 kcal mol−1. Our analysis suggests that decreasing the solvent effect, arylation of enolates with unactivated arenes could become possible.

Crystal lattice free volume in a study of initiation reactivity of nitramines: Friction sensitivity

The relationship between friction sensitivity (FS) and the crystal lattice free space per molecule, ΔV, of thirteen nitramines is described by a linear equation, divided into a number of the partial relationships with strong limitations by their molecular structure characteristics. Increasing FS due to raising of the ΔV values is not clearly confirmed. The influence of the ΔV values on friction sensitivity of nitramines is similar to that of their aza atoms which influence the mutual orientations of nitro groups in neighboring molecules. The dipole-dipole interaction of the oxygen and nitrogen atoms of nitro groups in neighboring nitramine molecules has a major effect on their own FS. In accordance with this interaction, a directly proportional relationship was derived between FS and the intrinsic gas phase molecular volume, Vint, of the nitramines mentioned, which is divided also into several straight lines according to relatively tight molecular structure similarity. The relationships found again confirm a level of disorder in the distribution of the forces in the crystal lattice of the “common” quality of ε−2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, in comparison with its reduced sensitivity (RS) or chemically pure analogue.

“Hole-catalyzed” cycloadditions of the gaseous ionized nitrile N-oxides Ph-C[tbnd]N+[sbnd]O[rad] and CH3[sbnd]C[tbnd]N+[sbnd]O[rad] with model dipolarophiles

In solution, pericyclic reactions have been shown to be greatly accelerated with near barrier-less energy surfaces and high efficiency as well as high stereo and regioselectivity by the use of reagents in their radical cation forms, that is, via “hole-catalyzed” cycloadditions. In this study, the intrinsic gas-phase [3++2] cycloaddition reactivity of two model nitrile N-oxides in their ionized forms, that is PhCN+O (1) and CH3CN+O (2) towards prototype dipolarophiles, that is several ketones, nitriles, and alkenes was investigated via pentaquadrupole MS3 mass spectrometry. The competition between hole-catalyzed [3++2] cycloaddition and electron and/or proton transfer was evaluated and compared to proton affinities and ionization energies. With alkenes and ethers, 1 was found to react exclusively via proton and/or electron transfer. But with nitriles and ketones, cycloaddition occurred predominantly to yield abundant cycloadducts. MS3 scans were used to probe the structures of the final products, whereas theoretical calculations served to evaluate the likehood of competing reactions. In great contrast to 1 and probably due to its greater acidity, 2 was found to react exclusively towards all dipolarophiles tested herein by either proton and/or electron transfer, or both.

Diffusion in sphere and spherical-cavity arrays with interacting gas and surface phases

Three-dimensional computations of coupled gas and surface diffusion in periodic arrays of solid spheres and spherical cavities are undertaken to assess the role of pore size, void fraction, and pore geometry on permeability. With nano-dimensioned pores, gas-phase diffusion is hindered by the small mean-free path, so the overall permeability hinges on surface diffusion. We prescribe the intrinsic gas-phase diffusivity to be self-consistent with the Knudsen diffusivity obtained from molecular-kinetic simulations reported in the literature. The continuum model of Albaalbaki and Hill then couples the gas and surface phases via an equilibrium adsorption isotherm and kinetic-exchange parameters. Solving these equations in complex pore-scale geometries provides new insights into the coupling. To interpret the results, we decompose the net flux into (i) gas and surface contributions that can be calculated without knowledge of the concentration perturbations to equilibrium, but which depend on the pore geometry, and (ii) counterparts that must be evaluated from integrals of the concentration perturbations to equilibrium. These measures are directly related to the familiar, but less precise, gas and surface tortuosity parameters, which are often used to interpret experiments. The results highlight (i) discontinuous variations in the fluxes when passing through void and solid percolation thresholds, (ii) how the surface flux depends on the specific surface area, and (iii) the pore sizes at which surface transport compares with void transport.

Flexible Acyclic Polyol-Chloride Anion Complexes and Their Characterization by Photoelectron Spectroscopy and Variable Temperature Binding Constant Determinations

Flexible acyclic alcohols with one to five hydroxyl groups were bound to a chloride anion and these complexes were interrogated by negative ion photoelectron spectroscopy and companion density functional theory computations. The resulting vertical detachment energies are reproduced on average to 0.10 eV by M06-2X/aug-cc-pVTZ predictions and range from 4.45-5.96 eV. These values are 0.84-2.35 eV larger than the adiabatic detachment energy of Cl(-) as a result of the larger hydrogen bond networks in the bigger polyols. Adiabatic detachment energies of the alcohol-Cl(-) clusters are more difficult to determine both experimentally and computationally. This is due to the large geometry changes that occur upon photodetachment and the large bond dissociation energy of H-Cl which enables the resulting chlorine atom to abstract a hydrogen from any of the methylene (CH2) or methine (CH) positions. Both ionic and nonionic hydrogen bonds (i.e., OH···Cl(-) and OH···OH···Cl(-)) form in the larger polyols complexes and are found to be energetically comparable. Subtle structural differences, consequently can lead to the formation of different types of hydrogen bonds, and maximizing the ionic ones is not always preferred. Solution equilibrium binding constants between the alcohols and tetrabutylammonium chloride (TBACl) in acetonitrile at -24.2, +22.0, and +53.6 °C were also determined. The free energies of association are nearly identical for all of the substrates (i.e., ΔG° = -2.8 ± 0.7 kcal mol(-1)). Compensating enthalpy and entropy values reveal, contrary to expectation and the intrinsic gas-phase preferences, that the bigger systems with more hydroxyl groups are entropically favored and enthalpically disfavored relative to the smaller species. This suggests that more solvent molecules are released upon binding TBACl to alcohols with more hydroxyl groups and is consistent with the measured negative heat capacities. These quantities increase with molecular complexity of the substrate, however, contrary to common interpretation of these values.

Superacidity of closo-dodecaborate-based Brønsted acids: a DFT study.

The structures and intrinsic gas-phase acidities (GA) of some dodecaborane acids, the derivatives of YB12H11H (Y = PF3, NH3, NF3, NMe3), B12H12H2, and B12H12H(-) (HA, H2A, and HA(-), respectively) have been computationally explored with DFT B3LYP method at the 6-311+G** level of theory as new possible directions of creating superstrong Brønsted acids. Depending on the nature and number of the substituents different protonation geometries were investigated. In general, the GA values of the neutral systems varied according to the substituents in the following order: CF3 < F < Cl and in case of anionic acids: CF3 < Cl < F. The dodecatrifluoromethyl derivative of H2A, B12(CF3)12H1H2, emerges as the strongest among the considered acids and is expected to be in the gas phase at least as strong as the undecatrifluoromethyl carborane, CB11(CF3)11H1H. The GA values of the respective monoanionic forms of the considered acids all, but the (CF3)11 derivative, remained higher than the widely used threshold of superacidity. The HA derivatives' (Y = PF3, NF3) GA's were approximately in the same range as the H2A acids'. In the case Y = NH3 or NMe3 the GA values were significantly higher. Also, the pKa values of B12H12H2, CB11H12H, and their perfluorinated derivatives in 1,2-dichloroethane (DCE) were estimated with SMD and cluster-continuum model calculations. The obtained estimates of pKa values of the perfluorinated derivatives are by around 30 units lower than that of trifluoromethylsulfonylimide, making these acids the strongest ever predicted in solution. The derivatives of B12H12H2 are as a rule not significantly weaker acids than the respective derivatives of CB11H12H. This is important for expanding practical applicability of this type of acids and their anions, as they are synthetically much more accessible than the corresponding CB11H12(-) derivatives.

Design and screening of suitable ligand/diluents systems for removal of Sr2+ ion from nuclear waste: Density functional theoretical modelling

Density functional theoretical (DFT) calculation has been used for the design and screening of ligand/solvent systems for the selective and efficient extraction of Sr2+ ion from aqueous solution using free energy analysis. Present DFT study has shown that the metal ion selectivity cannot be predicted using intrinsic gas phase interaction energy alone. Even implicit solvation employing conductor like screening model (COSMO) approach unable to predict the correct trend of experimental selectivity. The COSMO solvation model when used explicitly by considering first solvation sphere around the metal ion it captures the correct trend of experimental selectivity. Organic solvent of high dielectric constant was found to be suitable for the extraction of the metal ion. Further, COSMO for real solvent (COSMO-RS) was successfully used to predict the solubility and partition coefficients of the ligands for screening. Presence of nitrate anion in the complexation reaction was shown to increase the gas as well as solvent phase complexion energy. The calculated theoretical extraction energy was found to be well correlated to the experimentally observed distribution constant of Sr2+ ion in the biphasic systems. The preferential selectivity of Sr2+ ion over other competing ions towards macrocyclic ligands was demonstrated by calculating free energy of extraction in the biphasic systems. Natural bond order (NBO) analysis was also performed to investigate the nature of bonding in Sr2+ ion-crown ether interaction.

Unraveling Organocuprate Complexity: Fundamental Insights into Intrinsic Group Transfer Selectivity in Alkylation Reactions

The near thermal conditions of an ion-trap mass spectrometer were used to examine the intrinsic gas-phase reactivity and selectivity of nucleophilic substitution reactions. The well-defined organocuprate anions [CH3CuR](-) (R = CH3CH2, CH3CH2CH2, (CH3)2CH, PhCH2CH2, PhCH2, Ph, C3H5, and H) were reacted with CH3I. The rates (reaction efficiencies, ϕ) and selectivities (the product ion branching ratios) were compared with those of [CH3CuCH3](-) reacting with CH3I. Alkyl R groups yielded similar efficiencies, with selectivity for C-C bond formation at the coordinated R group. Inclusion of unsaturated R groups curbed the overall reactivity (ϕ = 1 to 2 orders of magnitude lower). With the exception of R = PhCH2CH2, these switched their selectivity to C-C bond formation at the CH3 group. Replacing an organyl ligand with R = H significantly enhanced the reactivity (8-fold), resulting in the selective formation of methane. Unique decomposition and side-reactions observed include: (1) spontaneous β-hydride elimination from [RCuI](-) byproducts; and (2) homocoupling of the pre-existing organocuprate ligands in [CH3CuC3H5](-), as shown by deuterium labeling. DFT (B3LYP-D/Def2-QZVP//B3LYP/SDD:6-31+G(d)) predicts that the alkylation mechanism for all species is via oxidative addition/reductive elimination (OA/RE). OA is the rate-limiting step, while RE determines selectivity: the effects of R on each were examined.

An experimental and numerical investigation of the hetero-/homogeneous combustion of fuel-rich hydrogen/air mixtures over platinum

The hetero-/homogeneous combustion of hydrogen/air mixtures over platinum was investigated experimentally and numerically in a channel-flow configuration at fuel-rich equivalence ratios ranging from 2 to 7, pressures up to 5bar and wall temperatures 760–1200K. Experiments involved in situ one-dimensional Raman measurements of major gas-phase species concentrations over the catalyst boundary layer and planar laser induced fluorescence (LIF) of the OH radical, while simulations included an elliptic 2-D model with detailed heterogeneous and homogeneous reaction mechanisms. The employed reaction schemes reproduced the measured catalytic reactant consumption, the onset of homogeneous ignition, and the post-ignition flame shapes at all examined conditions. Although below a critical pressure, which depended on temperature, the intrinsic gas-phase kinetics of hydrogen dictated lower reactivity for the fuel-rich stoichiometries when compared to fuel-lean ones, homogeneous ignition was still more favorable for the rich stoichiometries due to the lower molecular transport of the deficient oxygen reactant that resulted in modest catalytic reactant consumption over the gaseous induction zone. Above the critical pressure, the intrinsic gaseous hydrogen kinetics yielded higher reactivity for the rich stoichiometries, which resulted in vigorous gaseous combustion at pressures up to 5bar, in contrast to lean stoichiometry studies whereby homogeneous combustion was altogether suppressed above 3bar. Computations at fuel-rich stoichiometries in practical channel geometries indicated that homogeneous combustion was not of concern for reactor thermal management, since the larger than unity Lewis number of the deficient oxygen reactant confined the flames to the core of the channel, away from the solid walls.

Ring Strain and Other Factors Governing the Basicity of Nitrogen Heterocycles – An Interpretation by Triadic Analysis

M06-2X/6–311++G(2df, 2pd)//M06–2X/6–31+G(d) computations were employed to investigate the intrinsic gas phase basicity of strained nitrogen heterocycles involving aziridine, azetidine, pyrrolidine and piperidine, together with their N- methyl and N-phenyl derivatives, NR(CH2)n (n = 2– 5 ; R = H, Me and Ph). Basicity constants were compared with the corresponding acyclic counterparts, NR(CH3)2 (R = H, Me and Ph), and were, based on triadic analysis, resolved into contributions mirroring features of both initial base and the final protonated form as well as their interplay, thus offering quantitative insight into the obtained results. In general, the N-methyl derivatives provided strongest bases investigated here, and, within each group of molecules, the basicity increased on going from three- to six-membered rings, consistent with a decrease in ring strain, with four-membered systems already surpassing or coming close to the basicity of the acyclic gauge molecule. Calculated basicities were found in a very good agreement with available experimental data, except for N– methylazetidine, where a remarkable discrepancy was revealed, suggesting that this system should be experimentally reassessed and its gas-phase basicity parameters revised. Triadic analysis showed different behaviour of individual contributions governing basicities, both among and within distinct families of molecules. It also convincingly demonstrated that, if a proper and a quantitatively accurate interpretation of observed basicity trends is desired, one should not rely only on concepts such as localized reactive hybrid orbitals (RHO) or thus derived nitrogen electron-donating ability (T. Ohwada et al., J. Org. Chem. 69 (2004) 7486), which take into account only properties of the initial base in question, but rather consider protonation reaction in its entirety.

A quantitative study of intrinsic non-covalent interactions within complexes of α-cyclodextrin and benzoate derivatives

A novel deconvolution method for energy-resolved reaction cross sections is applied to determine intrinsic gas-phase dissociation energies for non-covalent α-cyclodextrin host-guest complexes. M06-2X//M06-L/6-31+G(d,p) calculations reproduce the experimental results and enable us to quantify the contribution of intermolecular hydrogen bonding.

Understanding the role of base stacking in nucleic acids. MD and QM analysis of tandem GA base pairs in RNA duplexes

Preceding NMR experiments show that the conformation of tandem GA base pairs, an important recurrent non-canonical building block in RNA duplexes, is context dependent. The GA base pairs adopt "sheared" N3(G)-N6(A), N2(G)-N7(A) geometry in the r(CGAG)(2) and r(iGGAiC)(2) contexts while switching to "imino" N1(G)-N1(A), O6(G)-N6(A) geometry in the r(GGAC)(2) and r(iCGAiG)(2) contexts (iC and iG stand for isocytosine and isoguanine, respectively). As base stacking is likely to be one of the key sources of the context dependence of the conformation of GA base pairs, we calculated base stacking energies in duplexes containing such base pairs, to see if this dependence can be predicted by stacking energy calculations. When investigating the context dependence of the GA geometry two different conformations of the same duplex were compared (imino vs. sheared). The geometries were generated via explicit solvent MD simulations of the respective RNA duplexes, while the subsequent QM energy calculations focused on base stacking interactions of the four internal base pairs. Geometrical relaxation of nucleobase atoms prior to the stacking energy computations has a non-negligible effect on the results. The stacking energies were derived at the DFT-D/6-311++G(3df,3pd) level. We show a rather good correspondence between the intrinsic gas-phase stacking energies and the NMR-determined GA geometries. The conformation with more favorable gas-phase stacking is in most cases the one observed in experiments. This correlation is not improved when including solvent effects via the COSMO method. On the other side, the stacking calculations do not predict the relative thermodynamic stability of duplex formation for different sequences.