Effect of cation size and charge on the interaction between silica surfaces in 1:1, 2:1, and 3:1 aqueous electrolytes

Application of two complementary AFM measurements, force vs separation and adhesion force, reveals the combined effects of cation size and charge (valency) on the interaction between silica surfaces in three 1:1, three 2:1, and three 3:1 metal chloride aqueous solutions of different concentrations. The interaction between the silica surfaces in 1:1 and 2:1 salt solutions is fully accounted for by ion-independent van der Waals (vdW) attraction and electric double-layer repulsion modified by cation specific adsorption to the silica surfaces. The deduced ranking of mono- and divalent cation adsorption capacity (adsorbability) to silica, Mg(2+) < Ca(2+) < Na(+) < Sr(2+) < K(+) < Cs(+), follows cation bare size as well as cation solvation energy but does not correlate with hydrated ionic radius or with volume or surface ionic charge density. In the presence of 3:1 salts, the coarse phenomenology of the force between the silica surfaces as a function of salt concentration resembles that in 1:1 and 2:1 electrolytes. Nevertheless, two fundamental differences should be noticed. First, the attraction between the silica surfaces is too large to be attributed solely to vdW force, hence implying an additional attraction mechanism or gross modification of the conventional vdW attraction. Second, neutralization of the silica surfaces occurs at trivalent cation concentrations that are 3 orders of magnitude smaller than those characterizing surface neutralization by mono- and divalent cations. Consequently, when trivalent cations are added to our cation adsorbability series the correlation with bare ion size breaks down abruptly. The strong adsorbability of trivalent cations to silica contrasts straightforward expectations based on ranking of the cationic solvation energies, thus suggesting a different adsorption mechanism which is inoperative or weak for mono- and divalent cations.     

Infrared spectroscopy of gas phase C3H5+ : the allyl and 2-propenyl cations

C3H5+ cations are probed with infrared photodissociation spectroscopy in the 800-3500 cm(-1) region using the method of rare gas tagging. The ions and their complexes with Ar or N2 are produced in a pulsed electric discharge supersonic expansion cluster source. Two structural isomers are characterized, namely, the allyl (CH2CHCH2+) and 2-propenyl (CH3CCH2+) cations. The infrared spectrum of the allyl cation confirms previous theoretical and condensed phase studies of the C(2nu) charge delocalized, resonance-stabilized structure. The 2-propenyl cation spectrum is consistent with a C(s) symmetry structure having a nearly linear CCC backbone and a hyperconjugatively stabilizing methyl group.     

Charge exchange in tandem mass spectrometry: dissociative single electron capture by doubly-charged toluene cations

Single electron capture by doubly-charged toluene cations upon collision with various target gases has been investigated by sector tandem mass spectrometry. Both non-dissociative and dissociative charge transfer reactions leading to C(7)H(7)(+) + H and to C(5)H(5)(+) + [C(2),H(3)] are detected. Seven atomic or molecular target gases have been used with ionisation energies ranging from 8.8 eV to 14 eV. The branching ratios between the different non-dissociative and dissociative exit channels have been determined as well as the translational energy release on the dissociation products. The experimental data are compared to the predictions of a two-state semi-classical theoretical model that takes into account the non-adiabatic transition responsible for the charge transfer reaction. A wide reaction window shows up but the internal energies of the C(7)H(8)(+) cations produced by single electron capture are observed to be larger than expected. We assign this effect partly to the influence of the large density of vibrational states and to the multichannel nature of the process. Excited states of the dication are also most probably involved in the charge exchange reaction.     

Metal cations toxicity: An inorganic interpretation

Chemical hardness is one of the useful parameters giving information about the toxic nature of the structures. In the present work, absolute chemical hardness imparted to the science by Pearson, the hydration enthalpies, the element's electronegativity, as calculated by Batsanov (using the force constants of the bonds), the calculated electrostatic charge on the hydrated cations, the absolute radii for the metals and the effective nuclear charges, were correlated with available toxicology data for a series of metal cations (namely Hg²⁺, Cd²⁺, Cu²⁺ and K⁺) in order to obtain, from a physicochemical point of view, a better understanding of the deleterious actions of metal cations on living organisms. A series of linear curves and empirical equations were obtained, providing a convincing picture of the correlation toxicity-physical inorganic chemistry.     

1H- und 13C-NMR-spektroskopische Untersuchungen zur Ladungsverteilung in substituierten 1,3-Dioxan-2-ylium-Salzen

The ¹H and ¹³C NMR spectra of a series of 1,3-dioxan-2-ylium salts substituted at C-2 and C-4, C-5, C-6 have been measured. The atomic charge distribution in 1,3-dioxan- and 1,3-dioxolan-2-ylium cations has been calculated with the MINDO/3 method, leading to a linear correlation between π-charge and ¹³C chemical shift at C-2. The strong C-21-proton downfield shift is caused by the anisotropic influence of the mesomeric cation system. The conformations of substituted 1,3-dioxan-2-ylium cations are discussed.     

Reaction coordinate analysis of the S2-S1 internal conversion of phenylacetylene

The reaction coordinate of the S(2)-S(1) internal conversion (IC) of phenylacetylene (PA) was analyzed using the ab initio complete active space self-consistent field (CASSCF) method. In the first process after electronic excitation into S(2), the aromatic benzene ring is transformed into a nonaromatic quinoid structure. The ethynyl part (-C[triple bond]CH) takes an incomplete allenoid structure in which the CC bond elongates to an intermediate value between typical C[triple bond]C triple and C=C double bonds, but the bend angle of -CCH is 180 degrees . In the second process, PA takes a complete allenoid structure with an out-of-plane location of the beta-H atom (i.e., the H atom of the ethynyl part) and a further elongation of the CC bond so that PA is most stable in S(2) (S(2)-bent). The conical intersection between S(2) and S(1) (S(2)/S(1)-CIX) is located near the S(2)-bent geometry and is slightly unstable energetically. After transition at S(2)/S(1)-CIX, PA quickly loses both quinoid and allenoid structures and recovers the aromaticity of the benzene ring in S(1). Analysis of the dipole moment along the reaction coordinate shows that the weak electron-withdrawing group of the ethynyl part in S(0) suddenly changes into an electron-donating group in S(2) after the main transition of S(0)-S(2). The photoinduced change of the dipole moment is a driving force to the formation of a quinoid structure in S(2). Regarding the benefit of the reaction coordinate analysis of the multidimensional potential energy surfaces of PA, the present picture of the IC process is much more elaborate than our previous representation (Amatatsu, Y.; Hasebe, Y. J. Phys. Chem. A 2003 107, 11169-11173). Vibrational analyses along the reaction coordinate were also performed to support a time-resolved spectroscopic experiment on the S(2)-S(1) IC process of PA.     

The effect of metal cations on the nature of the first electronic transition of liquid water as studied by attenuated total reflection far-ultraviolet spectroscopy

The first electronic transition (?←X?) of liquid water was studied from the perspective of the hydration of cations by analyzing the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of the Group I, II, and XIII metal nitrate electrolyte solutions. The ?←X? transition energies of 1 M electrolyte solutions are higher (Li(+): 8.024 eV and Cs(+): 8.013 eV) than that of pure water (8.010 eV) and linearly correlate with the Gibbs energies of hydration of the cations. The increases in the ?←X? transition energies are mostly attributable to the hydrogen bond formation energies of water molecules in the ground state induced by the presence of the cations. The deviation from the linear relation was observed for the high charge density cations, H(+), Li(+), and Be(2+), which reflects that the electronic energies in the excited states are also perturbed. Quantum chemical calculations show that the ?←X? transition energies of the water-cation complexes depend on the hydration structures of the cations. The calculated ?←X? transition energies of the water molecules hydrating high charge density cations spread more widely than those of the low charge density cations. The calculated transition energy spreads of the water-cation complexes directly correlate with the widths of the ?←X? transition bands measured by ATR-FUV spectroscopy.     

Effect of ion-exchanged alkali metal cations on the photolysis of 2-pentanone included within ZSM-5 zeolite cavities: a study of ab initio molecular orbital calculations

The Norrish Type I and Type II reactions in the photolysis of 2-pentanone included within the alkali metal cation-exchanged ZSM-5 zeolite have been investigated by experimental and theoretical approaches. Changes in the molecular environment of the zeolite cavities by exchanging the cations had significant effects not only on the adsorption state but also on the photochemical reactions of the ketones included within the zeolite cavities. The yields of the photolysis decreased and the ratio of the Type I/Type II reactions increased, respectively, by changing the ion-exchanged cations from Cs⁺ to Li⁺. The observed IR and phosphorescence spectra of the adsorbed ketones and the ab initio molecular orbital calculations of this host-guest system indicate that the ketones interact with two different adsorption sites, i.e. the surface OH groups and alkali metal cations, while the interaction between the ketones and cations increased by changing the cations from Cs⁺ to Li⁺. Molecular orbital calculations were also carried out and indicated that the zeolite framework promotes the delocalization of the charge density of the alkali metal cations which can modify the interaction between the adsorbed ketones and cations, resulting in significant changes in the photolysis of these ketones.     

Exchanged Cations and Water during Reactions in Polypyrrole Macroions from Artificial Muscles

The movement of the bilayer (polypyrrole–dodecylbenzenesulfonate/tape) during artificial muscle bending under flow of current square waves was studied in aqueous solutions of chloride salts. During current flow, polypyrrole redox reactions result in variations in the volumes of the films and macroscopic bending: swelling by reduction with expulsion of cations and shrinking by oxidation with the insertion of cations. The described angles follow a linear function, different in each of the studied salts, of the consumed charge: they are faradaic polymeric muscles. The linearity indicates that cations are the only exchanged ions in the studied potential range. By flow of the same specific charge in every electrolyte, different angles were described by the muscle. The charge and the angle allow the number and volume of both the exchanged cations and the water molecules (related to a reference) between the film to be determined, in addition to the electrolyte per unit of charge during the driving reaction. The attained apparent solvation numbers for the exchanged cations were: 0.8, 0.7, 0.6, 0.5, 0.5, 0.4, 0.25, and 0.0 for Na⁺, Mg²⁺, La³⁺, Li⁺, Ca²⁺, K⁺, Rb⁺, and Cs⁺, respectively.     

Aromatic Charge Resonance Interaction Probed by Infrared Spectroscopy

Charge resonance is a strong attractive intermolecular force in aromatic dimer radical ions. Despite its importance, this fundamental interaction has not been characterized at high resolution by spectroscopy of isolated dimers. We employ vibrational infrared spectroscopy of cold aromatic pyrrole dimer cations to precisely probe the charge distribution by measuring the frequency of the isolated N?H stretch mode (ν_NH). We observe a linear correlation between ν_NH and the partial charge q on the pyrrole molecule in different environments. Subtle effects of symmetry reduction, such as substitution of functional groups (here pyrrole replaced by N‐methylpyrrole) or asymmetric solvation (here by an inert N₂ ligand), shift the charge distribution toward the moiety with lower ionization energy. This general approach provides a precise experimental probe of the asymmetry of the charge distribution in such aromatic homo‐ and heterodimer cations.     

A molecular dynamics computer simulation study of room-temperature ionic liquids. I. Equilibrium solvation structure and free energetics

Solvation in 1-ethyl-3-methylmidazolium chloride and in 1-ethyl-3-methylimidazolium hexafluorophosphate near equilibrium is investigated via molecular dynamics computer simulations with diatomic and benzenelike molecules employed as probe solutes. It is found that electrostriction plays an important role in both solvation structure and free energetics. The angular and radial distributions of cations and anions become more structured and their densities near the solute become enhanced as the solute charge separation grows. Due to the enhancement in structural rigidity induced by electrostriction, the force constant associated with solvent configuration fluctuations relevant to charge shift and transfer processes is also found to increase. The effective polarity and reorganization free energies of these ionic liquids are analyzed and compared with those of highly polar acetonitrile. Their screening behavior of electric charges is also investigated.     

Explicit ions condensation around strongly charged polyelectrolytes and spherical macroions: the influence of salt concentration and chain linear charge density. Monte Carlo simulations

The condensation of monovalent counterions and trivalent salt particles around strong rigid and flexible polyelectrolyte chains as well as spherical macroions is investigated by Monte Carlo simulations. The results are compared with the condensation theory proposed by Manning. Considering flexible polyelectrolyte chains, the presence of trivalent salt is found to play an important role by promoting chain collapse. The attraction of counterions and salt particles near the polyelectrolyte chains is found to be strongly dependent on the chain linear charge density with a more important condensation at high values. When trivalent salt is added in a solution containing monovalent salt, the trivalent cations progressively replace the monovalent counterions. Ion condensation around flexible chains is also found to be more efficient compared with rigid rods due to monomer rearrangement around counterions and salt cations. In the case of spherical macroions, it is found that a fraction of their bare charge is neutralized by counterions and salt cations. The decrease of the Debye length, and thus the increase of salt concentration, promotes the attraction of counterions and salt particles at the macroion surface. Excluded volume effects are also found to significantly influence the condensation process, which is found to be more important by decreasing the ion size.     

Sensitivity of charge transfer reactions to hydrocarbon ion structures

Charge transfer reactivities of hydrocarbon ions have been measured with time-of-flight techniques, and results correlated with theoretical structures computed by self-consistent field molecular orbital methods. Recombination energies, ion structures, heats of formation, reaction energetics and relative charge transfer cross-sections are presented for molecular and fragment ions produced by electron bombardment ionization of CH₄, C₂H₄, C₂H₆, C₃H₈ and C₄H₁₀ molecules. Even-electron bridged cations have low ion recombination energies and relatively low charge transfer cross-sections as compared with odd-electron hydrocarbon cations.     

Multiphoton processes of CO at 230 nm

High resolution kinetic energy release spectra were obtained for C(+) and O(+) from CO multiphoton ionization followed by dissociation of CO(+). The excitation was through the CO (B (1)Sigma(+)) state via resonant two-photon excitation around 230 nm. A total of 5 and 6 photons are found to contribute to the production of carbon and oxygen cations. DC slice and Megapixel ion imaging techniques were used to acquire high quality images. Major features in both O(+) and C(+) spectra are assigned to the dissociation of some specific vibrational levels of CO(+)(X (2)Sigma(+)). The angular distributions of C(+) and O(+) are very distinct and those of various features of C(+) are also different. A dramatic change of the angular distribution of C(+) from dissociation of CO(+)(X (2)Sigma(+), nu(+) = 1) is attributed to an accidental one-photon resonance between CO(+)(X (2)Sigma(+), nu(+) = 1) and CO(+)(B (2)Sigma(+), nu(+) = 0) and explained well by a theoretical model. Both kinetic energy release and angular distributions were used to reveal the underlying dynamics.     

Hydrolysis versus ion correlation models in electrokinetic charge inversion: establishing application ranges

In this article, we investigate experimentally a wide range of situations where charge inversion (i.e., overcompensation of the surface charge of a colloidal particle by the countercharge) can occur. To that end, the electrophoretic mobility of sodium montmorillonite, silica, and polystyrene latex as functions of pH and concentration of different salts is presented, and conditions are established where charge inversion occurs. The reason for this study is to provide experimental evidence for distinguishing between two existing models for the explanation of charge inversion. One of these is the specific adsorption of ions located in the Stern layer in combination with a Gouy-Chapman diffuse part of the double layer. The other ion-correlation theories explain the phenomenon in terms of purely physical arguments based on Coulombic pair interactions between ions and surface charges and on excluded volume effects. In distinguishing between these two interpretations, the influence of the pH plays a central role because of its effect on the hydrolysis of multivalent cations. In our experiments, it is found that although 1-2 and 2-2 electrolytes provoke a decrease in the absolute values of the electrophoretic mobilities when their concentration in solution is increased, they never lead to charge inversion, whatever the surface charge or the pH. However, in the case of salts of trivalent cations, electrokinetic charge reversal is often observed above a certain critical electrolyte concentration. In addition, the extent of overcharging increases when the concentration is raised above the critical value. This trend occurs for any system in which the surface charge is pH-independent, as in polystyrene latex and montmorillonite. Most of the results presented here are compatible with the specific adsorption of hydrolyzed metal ions as the main driving force for charge inversion. At low pH, when the hydrolysis of trivalent cations is likely to be absent, overcharging can be attributed to ion correlation effects.     

Isomeric active ends of growing chains in the cationic polymerization of 4-methyl-1-pentene

Quantum chemical investigation of the relative stabilities of carbenium ions modelling the end units of growing chains in the cationic polymerization of 4-methyl-1-pentene has been carried out. The investigation was performed by the CNDO/2 method and by partial optimization of geometry. It is shown that the polymer chain can be adequately modelled by a methyl group. The calculated values of relative energies ΔE, geometric parameters and charge distribution are given for free cations, ion-pairs and for the cation-electron donor and cation-electron acceptor systems (H₂O, HCN and NO₂). All the additives show donor behaviour with respect to cations. The differences in the energies of secondary and tertiary cations decrease on going from free ions to ion-pairs or cation-additive molecule system.     

Role of metal co-cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

First principle calculations based on density functional theory are conducted to investigate the influence of metal cations including Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, La (OH)²⁺ and Ce (OH)²⁺ in the small cage of zeolite on the electronic environment of adjacent active center, Cu⁺ in CuY zeolite as well as the process of CO insertion into CH₃O to form CH₃OCO for oxidative carbonylation of methanol. The study explains the theoretical reasons for the effects of metal cations on the catalytic activity of zeolites. It was found that, the presence of co-cations in the small cage can affect the electronic properties and also the catalytic activity in two ways. Firstly, the presence of co-cations, viz., Ca²⁺, Sr²⁺, Mg²⁺, Ba²⁺ and La species in small cage hinders the migration of active Cu⁺ cations from the super cage to small cage. Secondly, the co-cations greatly affect the charge transfer from zeolite framework to Cu⁺ present in the adjacent super cage, leading to the increase of the net charge and binding energy of Cu⁺. The findings can improve the CO adsorption and insertion efficiencies, and the stability of transition states, which results in the enhanced catalytic activity of corresponding zeolites.     

Charge number effect on the miscibility of inorganic salt and surfactant in adsorbed film and micelle: Inorganic salt-dodecylammonium chloride mixtures

The effect of inorganic salts with different charge numbers of cations on the adsorption and micelle formation of dodecylammonium chloride (DAC) was clarified by applying the thermodynamic treatment of surfactant mixtures to mixtures of DAC with calcium and lanthanum chlorides and comparing the results with those of the sodium chloride-DAC mixture in the previous study. Surface tension of aqueous solutions of the salt-DAC mixture was measured as a function of the total molality of the mixture and the mole fraction of DAC in the mixture at 298.15 K under atmospheric pressure. Judging from the phase diagrams of adsorption and micelle formation obtained from the surface tension measurement, dodecylammonium cations expel inorganic cations from the adsorbed film and micelle and the repulsive interaction between dodecylammonium and inorganic cations increases with increasing charge number of the inorganic cation.