Absolute Reaction Cross Sections Research Articles

Reactivity of the Ethenium Cation (C2H5+) with Ethyne (C2H2): A Combined Experimental and Theoretical Study.

The gas-phase reaction between the ethyl cation (C2H5+) and ethyne (C2H2) is re-investigated by measuring absolute reactive cross sections (CSs) and branching ratios (BRs) as a function of collision energy, in the thermal and hyperthermal energy range, via tandem-guided ion beam mass spectrometry under single collision conditions. Dissociative photoionization of C2H5Br using tuneable VUV radiation in the range 10.5-14.0 eV is employed to generate C2H5+, which has also allowed us to explore the impact of increasing (vibrational) excitation on the reactivity. Reactivity experiments are complemented by theoretical calculations, at the G4 level of theory, of the relative energies and structures of the most relevant stationary points on the reactive potential energy hypersurface (PES) and by mass-analyzed ion kinetic energy (MIKE) spectrometry experiments to probe the metastable decomposition from the [C4H7]+ PES and elucidate the underlying reaction mechanisms. Two main product channels have been identified at a centre-of-mass collision energy of ∼0.1 eV: (a) C3H3++CH4, with BR = 0.76±0.05 and (b) C4H5++H2, with BR = 0.22±0.02. A third channel giving C2H3+ in association with C2H4 is shown to emerge at both high internal excitation of C2H5+ and high collision energies. From CS measurements, energy-dependent total rate constants in the range 4.3×10-11-5.2×10-10 cm3·molecule-1·s-1 have been obtained. Theoretical calculations indicate that both channels stem from a common covalently bound intermediate, CH3CH2CHCH+, from which barrierless and exothermic pathways exist for the production of both cyclic c-C3H3+ and linear H2CCCH+ isomers of the main product channel. For the minor C4H5+ product, two isomers are energetically accessible: the three-member cyclic isomer c-C3H2(CH3)+ and the higher energy linear structure CH2CHCCH2+, but their formation requires multiple isomerization steps and passages via transition states lying only 0.11 eV below the reagents' energy, thus explaining the smaller BR. Results have implications for the modeling of hydrocarbon chemistry in the interstellar medium and the atmospheres of planets and satellites as well as in laboratory plasmas (e.g., plasma-enhanced chemical vapor deposition of carbon nanotubes and diamond-like carbon films).

Absolute dissociation cross sections for D2 dissociation on Pt steps

Reaction mechanisms following gas-surface collisions may differ depending on the site of impact. On stepped Pt surfaces at least three dissociation mechanisms have been suggested to occur in parallel. Using supersonic molecular beams and a curved Pt single crystal, we unravel these site-dependent contributions and quantify absolute reaction cross sections using these mechanisms’ different dependencies on kinetic energy in the range of 0.7 to 13.4 kJ/mol. A sum of three dissociation mechanism probabilities fits our data well and allows us to extract absolute cross sections for indirect and direct non-activated dissociation at steps. We find good agreement with theoretical predictions.

State-selected ion-molecule reactions with VUV synchrotron radiation : the O2 + + C3H6 case

SynopsisO2 + molecular ion is produced by photoionization close to threshold at SOLEIL, DESIRS beam line. By means of coincidence methods, ions are prepared in selected vibrational and electronic states (X, v=0,3,15 and a, v=3). Their reactivity with the propene in single collision regime is studied in the guided ion beam in-strument CERISES, adding ability to vary the collision energy. Absolute reaction cross section and branching ratio are recorded for the 5 most intense reactive channels, described as dissociative charge transfer. Contrasted effects of internal and collision energy are observed.

Effects of collision energy and vibrational excitation of CH3+ cations on its reactivity with hydrocarbons: But-2-yne CH3CCCH3 as reagent partner.

The methyl carbocation is ubiquitous in gaseous environments, such as planetary ionospheres, cometary comae, and the interstellar medium, as well as combustion systems and plasma setups for technological applications. Here we report on a joint experimental and theoretical study on the mechanism of the reaction CH3+ + CH3CCCH3 (but-2-yne, also known as dimethylacetylene), by combining guided ion beam mass spectrometry experiments with ab initio calculations of the potential energy hypersurface. Such a reaction is relevant in understanding the chemical evolution of Saturn's largest satellite, Titan. Two complementary setups have been used: in one case, methyl cations are generated via electron ionization, while in the other case, direct vacuum ultraviolet photoionization with synchrotron radiation of methyl radicals is used to study internal energy effects on the reactivity. Absolute reactive cross sections have been measured as a function of collision energy, and product branching ratios have been derived. The two most abundant products result from electron and hydride transfer, occurring via direct and barrierless mechanisms, while other channels are initiated by the electrophilic addition of the methyl cation to the triple bond of but-2-yne. Among the minor channels, special relevance is placed on the formation of C5H7+, stemming from H2 loss from the addition complex. This is the only observed condensation product with the formation of new C-C bonds, and it might represent a viable pathway for the synthesis of complex organic species in astronomical environments and laboratory plasmas.

Dehydrohalogenation and Dehydration Reactions of i-C3H7Br and i-C3H7OH by Sodium Ions Studied by Guided Ion Beam Techniques and Quantum Chemical Methods.

Dehydrohalogenation and dehydration reactions of gas-phase i-C3H7Br and i-C3H7OH molecules induced by collision with Na(+), all participants being in their electronic ground state, were studied experimentally in our laboratory using a radiofrequency-guided ion beam apparatus and covering the 0.10-10.00 eV center of mass (CM) energy range. In Na(+) + i-C3H7Br collisions the formation of [C3H6-Na](+) and [HBr-Na](+) by dehydrohalogenation was observed and quantified, as well as that of the ion-molecule adduct [Na-i-C3H7Br](+) together with its decomposition products C3H7(+) and NaBr. In Na(+) + i-C3H7OH collisions the dehydration product [H2O-Na](+) was also found, while [C3H6-Na](+) was hardly detected. Moreover, the [Na-i-C3H7OH](+) adduct formation as well as its decomposition into C3H7(+) and NaOH were also quantified. For all these processes, absolute reaction cross sections were measured as a function of the CM collision energy. From measured excitation functions, rate constants for the formation of [C3H6-Na](+), [HBr-Na](+), and [H2O-Na](+) at 303 K were obtained. Complementing the experiments, exhaustive ab initio structure calculations at the MP2 level of theory were performed, giving information on the most relevant features of the potential energy surfaces (PESs) where the dehydrohalogenation, dehydration, and decomposition reactions take place adiabatically for both collision systems. On these PESs different stationary points associated with potential energy minima and transition state barriers were characterized, and their connectivity was ensured using the intrinsic-reaction-coordinate method. The main topology features of the ab initio calculated PESs allowed a qualitative interpretation of the experimental data also exposing the role of the sodium ion as a catalyst in elimination reactions.

What is limiting low-temperature atomic layer deposition of Al2O3? A vibrational sum-frequency generation study

The surface reactions during atomic layer deposition (ALD) of Al2O3 from Al(CH3)3 and H2O have been studied with broadband sum-frequency generation to reveal what is limiting the growth at low temperatures. The –CH3 surface coverage was measured for temperatures between 100 and 300 °C and the absolute reaction cross sections, describing the reaction kinetics, were determined for both half-cycles. It was found that –CH3 groups persisted on the surface after saturation of the H2O half-cycle. From a direct correlation with the growth per cycle, it was established that the reduced reactivity of H2O towards –CH3 is the dominant factor limiting the ALD process at low temperatures.

Separating Catalytic Activity at Edges and Terraces on Platinum: Hydrogen Dissociation

Heterogeneous catalysis relies to a large extent on the reactivity of metal nanoparticles. The surface of these particles consists of atomically smooth terraces and edges. As local environments of atoms in edges and terraces are different, their catalytic ability varies. This severely complicates accurate predictions of reaction kinetics in heterogeneous catalysis. In this study, we use the reaction dynamics of H2 dissociation on a series of [n(111) × (100)] stepped platinum single-crystal surfaces to resolve how reactivity for atoms in edges and terraces can be separated and quantified individually. A simple reactivity model that only requires input from n = 3 accurately predicts reactivity for any combination of a (100) step with a (111) terrace over the entire energy range of interest for incident molecules. Our results support the assumption in theoretical kinetics studies that the smallest unit cell accurately models the essential features of the catalytic surface, and we discuss limitations to this assumption. Finally, from our model, we quantify for the first time the absolute reaction cross section for a direct dissociative process in a gas–surface collision.

Dyson treatment of NFT medium polarization processes in superfluid nuclei

We discuss the solution of the Dyson equation (also known as the Nambu-Gor'kov equation) for the case of medium polarization Nuclear Field Theory (NFT) processes in nuclei, and apply it to the nucleus 120Sn. Starting from a mean field obtained with the Sly4 effective nucleon-nucleon force, (mk = 0.7), we renormalize the single-particle states and the pairing interaction through the coupling to collective vibrations of the system, obtaining a detailed description of the fragmentation of the quasiparticle strength and of the state-dependent pairing gap. These quantities are calculated in term of one- and two-particle spectroscopic amplitudes, amplitudes which can be used to calculate both one- and two-nucleon absolute transfer reaction cross sections to be directly confronted with the experimental findings.

Experimental studies of the dissociative recombination processes for the C6D6+and C6D7+ions

We have investigated the dissociative recombination (DR) of the C 6 D 6 + and C 6 D 7 + ions using the CRYRING heavy-ion storage ring at Stockholm University, Sweden. The dissociative recombination branching ratios were determined at minimal collision energy, showing that the DR of both ions was dominated by pathways keeping the carbon atoms together in one product. The absolute reaction cross sections for the titular ions are best fitted by σ (E cm [eV]) = 1.3 ± 0.4 × 10 -15 (E cm [eV]) −1.19 ± 0.02 cm 2 (C 6 D 6 + ) and σ (E cm [eV]) = 1.1 ± 0.3 × 10 -15 (E cm [eV]) −1.33 ± 0.02 cm 2 (C 6 D 7 + ) in the intervals 3-300 meV and 3-200 meV respectively. The thermal rate constants of the titular reactions are best described by: k(T) = 1.3 ± 0.4 × 10 -6 (T/300) −0.69 ± 0.02 cm 3 s -1 for C 6 D 6 + and k(T) = 2.0 ± 0.6 × 10 -6 (T/300) −0.83 ± 0.02 cm 3 s -1 for C 6 D 7 + . These expressions correlates well with earlier flowing afterglow studies on the same process.

A guided-ion beam study of the reactions of Xe+ and Xe2+ with NH3 at hyperthermal collision energies

We have measured the absolute cross sections for reactions of Xe(+) and Xe(2+) with NH(3) at collision energies in the range from near-thermal to ∼34 and ∼69 eV, respectively. For Xe(+), the cross section for charge transfer, the only exothermic channel, decreases from ∼200Å(2) below 0.1 eV to ∼12Å(2) at the highest energies studied. The production of NH(3) (+) is the only channel observed below 5 eV, above which a small amount of NH(2) (+) is also formed. In Xe(2+) reactions, the main products observed are NH(3) (+) and NH(2) (+). The charge transfer cross section decreases monotonically from ∼80 to ∼6Å(2) over the studied energy range. The NH(2) (+) cross section is similar to the charge transfer cross section at the lowest energies, and exhibits a second component above 0.4 eV, with a maximum of 65Å(2) at 0.7 eV, above which the cross section decreases to ∼30Å(2) at the highest energies studied. At energies above 10 eV, a small amount of NH(+) is also observed in Xe(2+) collisions. Product recoil velocity distributions were determined at selected collision energies, using guided-ion beam time-of-flight methods.

Hyperthermal atomic oxygen source for near-space simulation experiments

A hyperthermal atomic oxygen (AO) beam facility has been developed to investigate the collisions of high-velocity AO atoms with vapor-phase counterflow. Application of 4.5 kW, 2.4 GHz microwave power in the source chamber creates a continuous discharge in flowing O(2) gas. The O(2) feedstock is introduced into the source chamber in a vortex flow to constrain the plasma to the center region, with the chamber geometry promoting resonant excitation of the TM(011) mode to localize the energy deposition in the vicinity of the aluminum nitride (AlN) expansion nozzle. The approximately 3500 K environment serves to dissociate the O(2), resulting in an effluent consisting of 40% AO by number density. Downstream of the nozzle, a silicon carbide (SiC) skimmer selects the center portion of the discharge effluent, prior to the expansion reaching the first shock front and rethermalizing, creating a beam with a derived 2.5 km s(-1) velocity. Differential pumping of the skimmer chamber, an optional intermediate chamber and reaction chamber maintains a reaction chamber pressure in the mid-10(-6) to mid-10(-5) Torr range. The beam has been characterized with regard to total AO beam flux, O(2) dissociation fraction, and AO spatial profile using time-of-flight mass spectrometric and Kapton-H erosion measurements. A series of reactions AO+C(n)H(2n) (n=2-4) has been studied under single-collision conditions using mass spectrometric product detection, and at higher background pressure detecting dispersed IR emissions from primary and secondary products using a step-scan Michelson interferometer. In a more recent AO crossed-beam experiment, number densities and predicted IR emission intensities have been modeled using the direct simulation Monte Carlo technique. The results have been used to guide the experimental conditions. IR emission intensity predictions are compared to detected signal levels to estimate absolute reaction cross sections.

Effects of Bending and Bending Angular Momentum on Reaction of NO2+ with C2H2: A Quasi-Classical Trajectory Study

A large set of quasi-classical trajectories were calculated at the PBE1PBE/6-311G** level of theory, in an attempt to understand the mechanistic origins of the large, mode-specific enhancement of the O-transfer reaction by NO2+ bending vibration and the surprisingly large suppressing effect of bending angular momentum. The trajectories reproduce the magnitude of the absolute reaction cross section, and also get the dependence of reactivity on NO2+ vibrational state, and the vibrational state dependent scattering behavior qualitatively correct. Analysis of the trajectories shows that the bending effect is not simply a consequence of enhanced reactivity in bent geometries but, rather, that excitation of bending motion allows reaction in a wider range of orientation angles, even if the NO2+ is not bent at the onset of the collisional interaction. There is a strong interplay between NO2+ bending and transient charge transfer during the collisions. Such charge transfer enhances reactivity, but only if the reactants are oriented correctly.

Experimental determination of dissociative recombination reaction pathways and absolute reaction cross-sections of CH2OH + , CD2OD + and CD2

(2007). Experimental determination of dissociative recombination reaction pathways and absolute reaction cross-sections of CH2OH + , CD2OD + and CD2. Molecular Physics: Vol. 105, A Special Issue In Honour of John M. Brown, pp. 899-906.

Laser Spectroscopic Excitation Function and Reaction Threshold Studies of the H + DCl → HCl + D Gas-Phase Isotope Exchange Reaction

The dynamics of the gas-phase hydrogen atom exchange reaction H + DCl --> HCl + D were studied using the pulsed laser photolysis/laser induced fluorescence "pump-and-probe" method. Laser photolysis of H2S at 222 nm was used to generate nonequilibrium distributions of translationally excited hydrogen atoms at high dilution in a flowing moderator gas (Ar)/reagent (DCl) mixture. H and D atoms were detected with sub-Doppler resolution via Lyman-alpha laser induced fluorescence spectroscopy, which allowed the measurement of the line shapes of the moderated H atom Doppler profiles as well as the concentration of the D atoms produced in the H + DCl --> HCl + D reaction. From the measured H atom Doppler profiles, the time evolution of the initially generated nascent nonequilibrium H atom speed distribution toward its room-temperature thermal equilibrium form was determined. In this way, the excitation function and the reaction threshold (E0 = 0.65 +/- 0.13 eV) for the H + DCl --> HCl + D reaction could be determined from the measured nonequilibrium D atom formation rates and single collision absolute reaction cross-section values of 0.12 +/- 0.04 A2 and 0.45 +/- 0.11 A2 measured at reagent collision energies of 1.0 and 1.4 eV, respectively.

State-selected C 2H 2+ + C 2H 4 reaction: Controlled by dynamics or statistics?

The reaction between acetylene ion and ethylene is revisited to investigate possible dynamical effects in one of the reactions, which are considered as benchmark systems for statistical models. Reactant ions are produced by photoionisation with synchrotron radiation and are selected in internal energy by a coincidence method between threshold photoelectrons and photoions. Measured absolute reaction cross-sections decrease with collision energy (0.1–1 eV CM), but increase with acetylene ion vibrational energy for the three exothermic channels giving C 4H 5 +, C 3H 3 + and C 2H 4 + ionic products. Even though RRKM calculations are shown to fit rather well experimental results for both the bimolecular (C 2H 2 + + C 2H 4) and unimolecular (C 4H 6 +) systems, some experimental results clearly indicate dynamical effects in this reaction for the C 2H 4 + production channel, in particular the strongly backward peaked C 2H 4 + angular distribution. We propose an alternative model combining reaction control both by dynamics and by statistics: the first step in the reactant approach is the capture between reactants, followed by a charge transfer process controlled by dynamics. In a second step, either the two reactants separate leading to C 2H 4 + ionic products, or there is a rearrangement into 1,3-butadiene (C 4H 6 +) ion which dissociates statistically into C 4H 5 + + H and C 3H 3 + + CH 3 products. Charge transfer is shown to be possible at intermediate intermolecular distances, slightly shorter than the capture distance, provided that one takes into account the charge–quadrupole interaction in addition to the ion-induced dipole interaction. This work clearly shows that a good fit of experimental data by RRKM calculations does not prove that the reaction elementary mechanism is controlled by statistics.

The mechanism of proton exchange: Guided ion beam studies of the reactions, H(H2O)n+ (n=1–4)+D2O and D(D2O)n+ (n=1–4)+H2O

Reactions of protonated water clusters, H(H2O)n+ (n=1–4) with D2O and their “mirror” reactions, D(D2O)n+ (n=1–4) with H2O, are studied using guided-ion beam mass spectrometry. Absolute reaction cross sections are determined as a function of collision energy from thermal energy to over 10 eV. At low collision energies, we observe reactions in which H2O and D2O molecules are interchanged and reactions where H-D exchange has occurred. As the collision energy is increased, the H-D exchange products decrease and the water exchange products become dominant. At high collision energies, processes in which one or more water molecules are lost from the reactant ions become important, with simple collision-induced dissociation processes, i.e., those without H-D exchange, being dominant. Threshold energies of endothermic channels are measured and used to determine binding energies of the proton bound complexes, which are consistent with those determined by thermal equilibrium measurements and previous collision-induced dissociation studies. A kinetic scheme that relies only on the ratio of isomerization and dissociation rate constants successfully accounts for the kinetic energy dependence observed in the branching ratios for H-D and water exchange products in all systems. Rice–Ramsperger–Kassel–Marcus theory and ab initio calculations confirm the feasibility and establish the details of this kinetic model.

Hyperthermal Reactions of O+(4S3/2) with CD4 and CH4: Theory and Experiment

Theoretical and experimental methods are applied to the study of the reaction dynamics in hyperthermal collisions of O+ (4S3/2) with methane. Measurements of the absolute reaction cross sections for the interaction of O+ with CD4 and CH4 were obtained at collision energies in the range from near-thermal to approximately 15 eV, using the guided-ion beam (GIB) technique. Product recoil velocity distributions, using the GIB time-of-flight (TOF) methods, were determined for several product ions at selected collision energies. The main reaction channel, charge transfer, proceeds via large impact parameter collisions. A number of minor channels, involving more intimate collisions, were also detected. Ab initio electronic structure calculations have been performed with different levels of theory and basis sets, including high-level coupled-cluster calculations to determine the energies of reaction intermediates and transition states for reaction. Several reaction paths on both quartet and doublet electronic states of (O·CH4)+ are found, and these provide a reasonable qualitative interpretation of the experiments. Although most of the products can be produced via spin-allowed pathways, the appearance of CH3+ at low energies suggests that intersystem crossing plays some role.

Reactions of O+ with CnH2n+2, n=2-4: a guided-ion beam study.

We have measured absolute reaction cross sections for the interaction of O(+) with ethane, propane, and n-butane at collision energies in the range from near thermal to approximately 20 eV, using the guided-ion beam (GIB) technique. We have also measured product recoil velocity distributions using the GIB time-of-flight (TOF) technique for several product ions at a series of collision energies. The total cross sections for each alkane are in excess of 100 A(2) at energies below approximately 2 eV, and in each case several ionic products arise. The large cross sections suggest reactions that are dominated by large impact parameter collisions, as is consistent with a scenario in which the many products derive from a near-resonant, dissociative charge-transfer process that leads to several fragmentation pathways. The recoil velocities, which indicate product ions with largely thermal velocity distributions, support this picture. Several product ions, most notably the C(2)H(3) (+) fragment for each of the alkanes, exhibit enhanced reaction efficiency as collision energy increases, which can be largely attributed to endothermic channels within the dissociative charge-transfer mechanism.

Extraordinary branching ratios in astrophysically important dissociative recombination reactions.

Branching ratios of the dissociative recombination reactions of the astrophysically relevant ions DCO+, N2H+ and DOCO+ (as substitute for HOCO+) have been measured using the CRYRING storage ring at the Manne Siegbahn Laboratory at the University of Stockholm, Sweden. For DCO+, the channel leading to D and CO was by far the most important one (branching ratio 0.88), only small contributions of the CD + O and OD + C product pathways (branching ratios 0.06 each) were recorded. In the case of N2H+ the surprising result of a break-up of the N-N bond to N and NH (branching ratio 0.64) was found with the branching ratio of the N2 + H product channel therefore displaying a branching ratio of only 0.36. In the case of DOCO+, the three-body break-up into D + O + CO dominated (branching ratio 0.68), whereas the contribution of the CO2 + H channel was only minute (0.05). The remaining share (branching ratio 0.27) was taken by the pathway leading to OH + CO. For the dissociative recombination of N2H+ and DOCO+ also absolute reaction cross sections were obtained in the collisional energy range between 0 and 1 eV. From these cross sections it was possible to work out the thermal rate constants, which were found to be k(T) = 1.0+/-0.1 x 10(-7) (T/300 K)(-0.51+/-0.02) cm3 s(-1) and k(T) = 1.2+/-0.1 x 10(-6) (T/300 K)(-0.64+/-0.02) cm3 S(-1) for N2H+ and DOCO+, respectively.

A theoretical study of the O( 1D) + CH 4 reaction II

The titled reaction is assumed to proceed via an insertion mechanism. Statistical branching ratios for various product channels are predicted with RRKM rate constants that are obtained based on ab initio calculations. A modified collision-complex model is utilized in the estimation of absolute reaction cross-sections for primary channels. The product energy partitions for H and H 2 formation pathways are obtained. Subsequently, the RRKM rate constants for secondary reactions are calculated with correction for the translational and rotational energies of primary products. The results give insight to reaction mechanism and provide probable explanations to disputes among previous experimental findings.