Rotational state populations and angular distributions on surface scattered molecules: No on graphite

Rotational state populations and angular distributions of NO molecules were determined after the scattering of a supersonic beam from a graphite surface at different surface temperatures. The angular distributions exhibit an isotropic and a specular part. The rotational population of the scattered molecules can be described by Boltzmann distributions with identical temperatures for both electronic ground states²Π_½ and²Π_3/2 and both scattering components. The rotational temperature agrees with the surface temperature below 170 K and converges to a constant value of 250 K for surface temperatures higher than 350 K.     

Dynamics of the barium-molecule system within large argon clusters

The effects of adding molecules on the LIF at 540 nm of a barium atom at the surface of an argon cluster (average size 420) has been investigated. We showed that molecules like ethanol,n-hexane and O₂ from stable complexes with ground state barium. In the case of molecules like N₂, CH₄ and SF₆, the collisional quenching of solvated Ba(¹ P) is observed. The large quenching rates obtained are interpreted by a surface mobility of the collisional partners. Moreover, we showed that this collisional quenching leads to the ejection of free Ba(³ P ₁).     

Carbon dioxide adsorption on carbon nanomaterials

The adsorption of CO₂ on a number of activated carbons, thermal carbon black, and oxide materials at 195 K was studied using static and dynamic techniques. The landing surface areas ω(CO₂) ≈ 0.19 nm² on thermal carbon black and the absolute values of sorption for P/P ₀ < 0.4 were determined. The density of adsorbed CO₂ in the micropore volume was estimated at ρ(CO₂) = 0.91 g/cm³. It was demonstrated that the previously found effect of a weakening of the sorption interaction of nitrogen molecules with thin-walled materials (which manifested itself in an analysis of sorption isotherms by a comparative method) was pronounced to a lesser degree for the sorption of CO₂. At the same time, the presence of supermicropores in activated carbon samples resulted in overestimated values of surface areas. A dynamic method was proposed to measure the spectra of CO₂ desorption at 195–260 K using a SORBI-MS system for evaluating the binding energy of sorbate molecules with the surface.     

Anab initio study of the molecules P2O and P2O+

Summary This paper presents a detailedab initio study of the molecules P₂O and P₂O⁺ at the Hartree-Fock, and Multi-Reference Single and Double Excitation Configuration Interaction levels. An analysis of the geometries and relative stabilities of both molecules is presented, together with a discussion of the dissociation channels and of the electronic spectrum of linear P₂O. The results for the ionic species P₂O⁺ suggest a cyclic geometry for this molecule, as indicated by the calculated vibrational frequencies. The calculations also indicate a surface crossing at a relatively low energy which might lead to P₂O dissociation and may hence be one of the factors contributing to the failure to detect it at room temperatures.     

Hydration of guanidinium depends on its local environment

Hydration of gaseous guanidinium (Gdm⁺) with up to 100 water molecules attached was investigated using infrared photodissociation spectroscopy in the hydrogen stretch region between 2900 and 3800 cm^–1. Comparisons to IR spectra of low-energy computed structures indicate that at small cluster size, water interacts strongly with Gdm⁺ with three inner shell water molecules each accepting two hydrogen bonds from adjacent NH₂ groups in Gdm⁺. Comparisons to results for tetramethylammonium (TMA⁺) and Na⁺ enable structural information for larger clusters to be obtained. The similarity in the bonded OH region for Gdm(H₂O)₂₀ ⁺ vs. Gdm(H₂O)₁₀₀ ⁺ and the similarity in the bonded OH regions between Gdm⁺ and TMA⁺ but not Na⁺ for clusters with <50 water molecules indicate that Gdm⁺ does not significantly affect the hydrogen-bonding network of water molecules at large size. These results indicate that the hydration around Gdm⁺ changes for clusters with more than about eight water molecules to one in which inner shell water molecules only accept a single H-bond from Gdm⁺. More effective H-bonding drives this change in inner-shell water molecule binding to other water molecules. These results show that hydration of Gdm⁺ depends on its local environment, and that Gdm⁺ will interact with water even more strongly in an environment where water is partially excluded, such as the surface of a protein. This enhanced hydration in a limited solvation environment may provide new insights into the effectiveness of Gdm⁺ as a protein denaturant.     

Surface areas of kaolin, α-Fe2O3 and hydroxy-Al montmorillonite

 Adsorption of eight organic molecules on kaolin, α-Fe₂O₃ and hydroxy-Al montmorillonite was studied to examine the effect of sorbate area on the values of the surface area of these materials. For each sorbent, the number of molecules at monolayer coverage per gram produced a single hyperbola when plotted as a function of the area occupied by an adsorbate. The equations of the hyperbolas are: NA=22.23 A ^0.098 for the kaolin, NA=53.70 A ^-0.399 for α-Fe₂O₃ and NA=161.81 A ^0.322 for the hydroxy-Al montmorillonite. These equations give accessible surface areas and not the true surface areas of the solids studied, which remain elusive. Received: 13 November 1997 Accepted: 24 January 1998     

Competition between reactivity and relaxation in free electron attachment to molecules

The reactivity of the C₆F₅X (X=F, Cl, Br, I) molecules following low energy (0–15 eV) electron attachment is studied in the gas phase under single collision conditions, free molecular clusters and condensed molecules by means of crossed beams and surface experiments. All four molecules exhibit a very prominent resonance for low energy electron attachment (<1 eV, attachment cross section >10⁻¹⁴ cm²). Under collision free conditions thermal electron capture generates long lived molecular parent anions C₆F₅X^−*. Along the line Cl, Br, I dissociation into X⁻+C₆F₅ and X+C₆F₅-increasingly competes until for X=1 only chemical fragmentation is observed on the mass spectrometric time scale. In free molecular clusters chemical fragmentation is quantitatively quenched at low energies in favour of associative attachment yielding undissociated, relaxed ions (C₆F₅X)⁻ _n,n≥1. A further dissociative resonance at 6.5 eV in C₆F₅Cl is considerably enhanched in clusters. If these molecules are finally condensed on a solid surface, one observes a prominent Cl⁻ desorption resonance at 6.5 eV. While the quantitative quenching of the chemical reactivity at low energies is due to the additional possibilities of energy dissipation under aggregation, the enhanched reactivity at 6.5 eV is interpreted by the conversion of a core excited open channel resonance in single molecules into a closed channel (Feshbach) resonance when it is coupled to environmental molecules.     

Predissociation dynamics of Ã-state ammonia probed by two-photon excitation spectroscopy

Electronically excited ND₃(A¯) molecules have been prepared by laser two-photon excitation on theA¯¹A″₂—X¯¹′₁ transition and monitored via their resulting short-lived emission. The earlier observation of Douglas that ND₃(A¯) molecules carrying one quantum of out-of-plane bending vibration ν′₂ are least susceptible to predissociation, is confirmed. ND₃(A¯) predissociation rates are found to be both vibronic and rovibronic level dependent. Both observations may be understood by considering the likely form of the potential energy surface for ND₃(A¯) molecules in the region of the D₂N—D dissociation coordinate. At short D₂N—D separations this surface exhibits a barrier. The presence of a conical intersection (involving the ND₃ ground state surface) further out along the dissociation coordinate has a crucial influence on the magnitude of this barrier. The envisaged form of theA¯-state potential energy surface also provides a qualitative rationale for all previous experimental findings concerning electronic branching ratios and energy disposal amongst the primary photofragments arising in the photodissociation ofA¯-state ammonia.     

Electrosorption of β-naphthol on graphite

Isotherms for the adsorption of β-naphthol from a buffered aqueous solution of 0.5 M K₂SO₄ onto graphite were detemrined over a range of potential of 1.27 V. The adsorbent was a packed bed of ?100 + 120 mesh graphite powder. Sufficient surface area was available to calculate accurately the amount adsorbed by measuring spectrophotometrically the change in adsorbate concentration in the bulk solution.At all potentials, a Langmuir adsorption isotherm, modified for the displacement of solvent molecules, was followed up to 60–65% of monolayer coverage. The ratio of projected areas of β-naphthol and water molecules was consistent with the experimentally derived number of solvent molecules displaced, six. The largest amount of adsorption observed, 2.5×10^?10 mol cm^?2, agreed with the calculated monolayer coverage of β-naphthol molecules lying in flat orientation on the graphite surface. Adsorption increased at more positive potentials. Over the range of potential investigated, the adsorbability constant increased sixfold. Desorption was only partially reversible.     

Effect of TiO2 modification with fluorine on the physicochemical properties and activity in the photocatalytic oxidation of pollutants in air under UV irradiation

The influence of the modification of the TiO₂ surface with F^? ions on the physicochemical properties of the catalysts and efficiency in the photooxidation of gaseous molecules under atmospheric conditions and under UV irradiation was studied by IR spectroscopy. The fluorine-containing samples adsorb more water molecules than unmodified TiO₂. The amount of adsorbed water increases with increasing content of surface fluoride ions. The fluorination of the TiO₂ surface first leads to the substitution of the terminal OH groups by F^? ions and to an increase in acidity of the bridging acidic OH groups remained on the surface. The modification also results in the structural rearrangement of the surface involving defective and surface Ti⁴⁺ sites. Fluorine modification increases the activity of TiO₂ in the photocatalytic oxidation of ethanol, acetaldehyde, acetic acid, and acetone. At the same time, benzene and H₂S are oxidized more rapidly on unmodified TiO₂. The presence of fluorine on the TiO₂ surface exerts almost no effect on the oxidation rate of chlorine-containing substrates C₃H₇Cl and C₂H₄Cl₂.

     

PHOTOCHEMISTRY ON SURFACES. EXCITED STATE BEHAVIOR OF RUTHENIUM TRIS(BATHOPHENANTHROLINE DISULFONATE) ON COLLOIDAL ALUMINA-COATED SILICA PARTICLES*

Abstract— The excited state behavior of an anionic ruthenium(II) complex, RuL₃^4-(L=bathophen-anthroline disulfonate), that is electrostatically bound to positively charged alumina-coated silica particles is investigated. The apparent association constant for the binding of RuL₃^4-to the particles is 1.2 × 10⁴M^-1. Surface photochemical processes result in decreased emission yields and multiexponential excited state decay. Excited state quenching by ground-state molecules is evident at high surface coverages. The non-exponential decay kinetics observed at low surface coverages can be attributed either to clustering of the RuL₃^4-molecules or photoionization promoted by Lewis acid sites on the particle surface.     

Sputtering induced recombination of nitrogen isotopes on tungsten

Adsorbed isotopic mixtures of ¹⁴N₂ and ¹⁵N₂ at low coverages on polycrystalline tungsten have been used as model systems for studying sputtering induced recombination during secondary ion mass spectrometry (SIMS). Earlier studies have shown that N₂ is completely dissociated on a W surface at low coverage. Thermal desorption spectroscopy (TDS) has been employed here to confirm this fact; our results show that complete isotopic mixing occurs. Adsorbed nitrogen can be sputtered as both atoms and molecules and sputtering induced recombination of adsorbate atoms increases as primary ion energy increases. Sputtering induced recombination is detected through isotopic mixing in SIMS. The data show that the dominant mechanism for sputtering of dimers (N₂) is not direct emission from the surface but rather a sputtering induced recombination mechanism.     

Stability of oxygen anions and hydrogen abstraction from methane on reduced SnO2 (110) surface

The stability of oxygen anions and the hydrogen abstraction from methane on a reduced SnO₂ (110) crystal surface have been studied theoretically using a point-charge model. The geometric and electronic structures for the present molecules are calculated by means of a hybrid Hartree–Fock/density functional method at the B3LYP/6-311+G(3df, 3pd) level of theory. The calculations of the energies on the point-charge model are performed using these optimized geometries. It is found that a low concentration of the active oxygen species O⁻ and O₂⁻ is expected on the reduced SnO₂ surface. The activation energies for the abstraction of hydrogen atom from methane on the reduced SnO₂ surface are obtained: 12 kcal/mol for O⁻ species and more than 48 kcal/mol for O₂⁻ species, indicating that O⁻ species on the surface is the main active center for the dissociation of a C(SINGLE BOND)H bond of methane, which is in agreement with the other oxide catalysts. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 669–678, 1998     

The state of metals in the Pt/Al2O3 and (Pt-Cu)/Al2O3 catalysts as indicated by IR spectroscopy with isotope dilution of 12C16O with 13C18O molecules

Adsorption of ¹³C¹⁸O+¹²C¹⁶O mixtures on the Pt(2.9%)/γ-Al₂O₃, (Pt(2.6%)+Cu(2.7%))/γ-Al₂O₃, and (Pt(2.6%)+Cu(5.1%))/γ-Al₂O₃ catalysts was studied by FTIR spectroscopy. On the metallic Pt surface at coverages close to saturation, CO is adsorbed both strongly and weakly to form linear species for which the vibrational frequencies of the isolated ¹³C¹⁸O molecules adsorbed on Pt are ∼1940 and ∼1970 cm⁻¹, respectively. The redistribution of intensities of the high-and low-frequency absorption bands in the spectra of adsorbed ¹³C¹⁸O indicates that these linear forms are present on the adjacent metal sites. The weak adsorption is responsible for the fast isotope exchange between the gaseous CO and CO molecules adsorbed on metal. The Pt-Cu alloys, in which the electronic state of the surface Pt atoms characteristic of monometallic Pt remains unchanged, are formed on the surface of the reduced Pt-Cu bimetallic catalysts. The decrease in the vibrational frequencies of the isolated C=O bonds in the isolated Pt-CO complexes suggests that the CO molecules adsorbed on the Cu atoms affect the electronic properties of Pt. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 831–836, May, 2007.     

Electrochemical and FTIR studies of -phenylalanine adsorption at the Au(111) electrode

The adsorption of -phenylalanine (Phe) at the Au(111) electrode surface has been studied using electrochemical techniques and subtractively normalized interfacial Fourier transform infrared (SNIFTIR) techniques. The electrochemical measurements of cyclic voltammetry, differential capacity and chronocoulometry were used to determine Gibbs energies of adsorption and the reference (E₁) and sample (E₂) potentials to be used in the spectroscopic measurements. The vibrational spectra have been used to determine: (i) the orientation of the molecule at the surface as a function of potential; (ii) the dependence of the band intensity on the surface coverage; (iii) the character of surface coordination, and (iv) the oxidation of adsorbed Phe molecules at positive potentials. The adsorption of Phe is characterized by ΔG values ranging from −18 to −37 kJ mol⁻¹ that are characteristic for a weak chemisorption of small aromatic molecules. The electrochemical and SNIFTIR measurements indicated that adsorbed Phe molecules change orientation as a function of applied potential. At the negatively charged surface Phe is predominantly adsorbed in the neutral form of the amino acid. At potentials positive to the pzc, adsorption occurs predominantly in the zwitterionic form with the ---COO⁻ group directed towards the surface and the ammonium group towards the solution. At more positive potentials electrocatalytic oxidation of Phe occurs and is marked by the appearance of the CO₂ asymmetric stretch band in the FTIR spectrum. Thus, relative to pzc, Phe is weakly chemisorbed at negative potentials, changes orientation at potentials close to the pzc and is oxidized at positive potentials.     

Amperometric Biosensor for Hydrogen Peroxide Based on Electrodeposited Sub-micrometer Gold Modified Glassy Carbon Electrode

IntroductionAmperometricbiosensorofhydrogenperoxideisofpracticalimportancebecauseofitswideapplicationsinchemical,biological,clinical,environmentalandmanyotherfields.Forimprovementofsensor抯quality,vari-ouskindsofchemicalmodificationmethodshavebeendevelopedforreducingredoxoverpotentialsofH2O2atelectrodesurfaces,increasingthedetectionsensitivity,linearrange,stabilityandlivetime.Ithasbeenshownthattheuseofsub-micrometersizedmetalparticlessuchasPt-blackcansignificantlyimprovethequalityofthebiosens…     

Solubilization and stabilization of fullerene C60 in presence of poly(vinyl pyrrolidone) molecules in water

Solubilizing C₆₀ molecules in an aqueous medium is highly imperative in processing them in different forms of ionic or nonionic liquids, nanofluids, films and other derivatives. In this investigation, we report a facile chemical route using polymer molecules of poly(vinyl pyrrolidone) (PVP) which mediate C₆₀ molecules dissolving in water in a stable solution at room temperature. Poly(vinyl pyrrolidone) molecules, soluble in water as well as many organic liquids such as n-butanol, ethanol, or DMF, can be useful for transferring C₆₀ molecules from a non-aqueous to an aqueous system. A broad optical absorption arises over 270–520 nm when C₆₀ molecules are dissolved in water, 0.001–0.065 g/L in presence of 20–120 g/L PVP molecules. It consists of a strong π → π* absorption band (relatively sharp) lying at 294 nm in C(sp²) electrons from PVP-surface modified C₆₀ molecules followed by a broad charge transfer band which extends up to 520 nm. Upon a suitable surface modification, the C₆₀ molecules conquer enhanced optical absorption in both kinds of the bands. Dynamic light scattering reveals an average hydrodynamic length 181.5 nm and a polydispersity index 0.506 after a typical loading 0.065 g/L C₆₀. A zeta potential ?8.3 mV with a surface conductivity 0.064 mS/cm at 6.5 pH describes a negatively charged surface structure, showing an n-electron transfer from C=O (PVP) to a nanosurface in surface modified C₆₀ molecules in a weak donor–acceptor complex. Water soluble C₆₀ in presence of a biocompatible compound like PVP is useful for biological, medicinal, and other applications.     

Electrochemistry of a carotenoid self-assembled monolayer

A carotenoid self-assembled monolayer was prepared by dipping a gold electrode into a solution of 4^′-thioxo-β,β-caroten-4-one in acetonitrile. Electrochemistry of the surface layer was investigated by cyclic voltammetry in an aqueous solution. No electrochemical reaction was detected in the potential region between 0.5 and −0.6 V vs. SCE. The anodic reaction of adsorbed carotenoid occurs at 0.8 V, whereas the irreversible anodic desorption proceeds at 1.4 V in 0.01 M HClO₄. Formation of the surface layer resulted in a decrease of the charging current as well as in a strong inhibition of the electron transfer reaction for species such as Fe(CN)₆³⁻, Ru(NH₃)₆³⁺, and dissolved oxygen. Prolonged voltage cycling in the O₂ reduction range induced some changes in the surface layer characteristics that were tentatively accounted for by the cross-linking of adsorbed molecules under the effect of transient oxygen radicals.     

Static secondary ionization mass spectrometry analysis of tributyl phosphate on mineral surfaces: Effect of Fe(II)

The static secondary ionization mass spectrometry (SIMS) spectrum of tri-n-butyl phosphate (TBP) on a variety of basalt and quartz samples is affected by the chemical composition of the mineral surface. When TBP is adsorbed on Fe(II)-bearing surfaces, the compound undergoes concomitant H^? abstraction and reduction, followed by the elimination of two C₄H₈ molecules to form an ion at m/z 137⁺. When TBP is adsorbed to quartz or other nonreducing surfaces, it merely undergoes protonation and elimination of three C₄H₈ molecules to form H₄PO ₄ ⁺ . When TBP is adsorbed to Fe(III)-bearing surfaces, it undergoes H^? abstraction and elimination of two C₄H₈ molecules, to form an ion at m/z 153⁺. These conclusions are supported by model studies that employed FeO, Fe₂0₃, TBP, and tributyl phosphite. The results show that the SIMS spectrum is very sensitive to the mode of TBP adsorption on the mineral surface.     

Molecular dynamics of electrosprayed water nanodroplets containing sodium bis(2‐ethylhexyl)sulfosuccinate

The behavior of aqueous solutions of sodium bis(2‐ethylhexyl)sulfosuccinate (AOTNa) subject to electrospray ionization (ESI) has been investigated by molecular dynamics (MD) simulations at three temperatures (350, 500 and 800 K). We consider several types of water nanodroplets containing AOTNa molecules and composed of a fixed number of water molecules (1000), N⁰_AOT AOT^? anions (N⁰_AOT = 0, 5, 10) and N⁰_Na sodium ions (N⁰_Na = 0, 5, 10, 15, 20): in a short time scale (less than 1 ns), the AOTNa molecules, initially forming direct micelles in the interior of the water nanodroplets, are observed in all cases to diffuse nearby the nanodroplet surface, so that the hydrophilic heads and sodium ions become surrounded by water molecules, whereas the alkyl chains lay at the droplet surface. Meanwhile, evaporation of water molecules and of solvated sodium ions occurs, leading to a decrease of the droplet size and charge. At 350 K, no ejection of neutral or charged surfactant molecules is observed, whereas at 500 K, some fragmentation occurs, and at 800 K, this event becomes more frequent. The interplay of all these processes, which depend on the values of temperature, N⁰_AOT and N⁰_Na eventually leads to anhydrous charged surfactant aggregates with prevalence of monocharged ones, in agreement with experimental results of ESI mass spectrometry. The quantitative analysis of the MD trajectories allows to evidence molecular details potentially useful in designing future ESI experimental conditions. Copyright © 2013 John Wiley & Sons, Ltd.