Dissociation Cross Sections Research Articles

Sodium Binding Interactions with Aliphatic Amino Acids: A Guided Ion Beam and Computational Study.

Metal binding affinities play a vital role in medicinal, biological, and industrial applications. In particular, metal cation-amino acid (AA) interactions contribute to protein stability such that analyzing analogous prototypical interactions is important. Here, we present a full description of the interactions of sodium cations (Na+) and six aliphatic amino acids (AA), where AA = glycine (Gly), alanine (Ala), homoalanine (hAla), valine (Val), leucine (Leu), and isoleucine (Ile). Experimentally, these interactions are evaluated using threshold collision-induced dissociation carried out in a guided ion beam tandem mass spectrometer, allowing for the determination of the kinetic-energy-dependent behavior of Na+-AA dissociation. Analysis of these dissociation cross sections, after accounting for multiple ion-molecule collisions, internal energy of reactant ions, and unimolecular decay rates, allows the determination of absolute Na+-AA bond dissociation energies (BDEs) in kJ/mol of Gly (164.0), Ala (166.9), hAla (167.9), Val (172.7), Leu (173.7), and Ile (174.6). These are favorably compared to quantum chemical calculations conducted at the B3LYP, B3P86, MP2(full), B3LYP-GD3BJ, and M06-2X levels of theory. Our combination of structural and energetic analyses provides information regarding the specific factors responsible for Na+ interactions with amino acids. Specifically, we find that the BDEs increase linearly with increasing polarizability of the amino acid.

Neutral dissociation of methane by electron impact and a complete and consistent cross section set

We present cross sections for the neutral dissociation of methane, in a large part obtained through analytical approximations. With these cross sections the work of Song et al (2015 J. Phys. Chem. Ref. Data 44 023101) can be extended, which results in a complete and consistent set of cross sections for the collision of electrons with up to 100 eV energy with methane molecules. Notably, the resulting cross section set does not require any data fitting to produce bulk swarm parameters that match with experiments. Therefore consistency can be considered an inherent trait of the set, since swarm parameters are used exclusively for validation of the cross sections. Neutral dissociation of methane is essential to include (1) because it is a crucial electron energy sink in methane plasma, and (2) because it largely contributes to the production of hydrogen radicals that can be vital for plasma-chemical processes. Finally, we compare the production rates of hydrogen species for a swarm-fitted data set with ours. The two consistent cross section sets predict different production rates, with differences of 45% (at 100 Td) and 125% (at 50 Td) for production of H2 and a similar trend for production of H. With this comparison we underline that the swarm-fitting procedure, used to ensure consistency of the electron swarm parameters, can possibly degrade the accuracy with which chemical production rates are estimated. This is of particular importance for applications with an emphasis on plasma-chemical activation of the gas.

Semiclassical theory of laser-assisted dissociative recombination

We study the process of laser-assisted dissociative recombination of an electron with a molecular cation using a semiclassical approach. In the region outside a reaction sphere the electron motion in the combined laser and Coulomb fields is treated classically. Within the sphere the laser-field effects are neglected, and the recombination probability is obtained from quantum-mechanical cross sections calculated for the laser-free process. Specific calculations are performed for dissociative recombination of ${\mathrm{H}}_{2}^{+}$ in the field of the intensity 2.09 GW/${\mathrm{cm}}^{2}$ and the wavelength $22.8\phantom{\rule{4pt}{0ex}}\ensuremath{\mu}\mathrm{m}$. In the energy region above 1 meV the cross section is significantly enhanced compared with the field-free case due to the Coulomb focusing effect. The influence of the indirect process due to electron capture into Rydberg states is also investigated. Although the Rydberg resonances are washed out due to the field effects, they influence significantly the magnitude of the dissociative recombination cross section.

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.

Vibrationally resolved ionization cross sections for the ground state and electronically excited states of the hydrogen molecule and its isotopomeres

An existing set of vibrationally resolved ionization cross section for the ground state and the first excited states of the hydrogen molecule, based on the Gryzinski method, is extended by cross sections for the isotopomeres of H2 (i.e. D2, T2, HD, HT, and DT), both for non-dissociative and dissociative ionizations. The comparison of cross sections for non-dissociative ionization of H2 with results obtained by the Molecular Convergent Close-Coupling method gives a very good agreement. The compiled tables give non-dissociative and dissociative cross sections for the ground state and the five energetically lowest electronically excited states of H2 and its isotopomeres, in each case for the first 9 vibrational levels. Data for all vibrational levels of the excited states is available online.

Thymidine and stavudine molecules in reactions with low-energy electrons

The negative ion formation and fragmentation processes in thymidine and stavudine were studied by means of resonant electron capture mass spectrometry in the electron energy range 0–14 eV. Stavudine is a nucleoside analog of thymidine, that differs from the latter by the presence of double bond in the deoxyribose moiety. In the energy range below 5 eV transient negative ions have been found to arise via shape resonances resulting in electron attachment into the empty π*-orbitals. The main fragmentation channels for molecular ions are the H-atom loss and N-glycosidic bond cleavage between sugar and a nucleobase moieties. The dissociative electron attachment cross sections for the fragment negative ions were measured. The structures for some observed anions and neutral counterparts were suggested basing on the thermochemical approach for dissociative reactions energy balance under the support of quantum chemical calculations. The processes of ion formation in thymidine were found to be similar to those revealed previously for deoxyuridine nucleoside. In contrast, very strong dissociative channel was found for stavudine yielding [M–R]– ions (where R is a sugar moiety) in the energy range <3 eV. The efficient fragmentation found for stavudine in the low energy electron attachment reactions may have implications for the design of nucleoside radiosensitizers for cancer therapy.

Resonant collisions of electrons with O2 via the lowest-lying 2Πg state of O2−

We report the results of an ab initio study of resonant vibrational excitation of molecular oxygen by electron impact at low energies where the lowest-lying ${}^{2}{\mathrm{\ensuremath{\Pi}}}_{g}$ resonant state of ${\mathrm{O}}_{2}^{\ensuremath{-}}$ dominantly contributes to the cross sections. The contribution of this resonance to the dissociative electron attachment cross section is also determined and the origin of its unusual oscillations is discussed. Calculations were performed within the nonlocal resonance model describing the nuclear dynamics of ${\mathrm{O}}_{2}^{\ensuremath{-}}$ after electron capture into the resonant state. The model was constructed using potential-energy curves obtained with standard quantum-chemical methods and eigenphase sums from the fixed-nuclei $R$-matrix calculations of electron scattering off ${\mathrm{O}}_{2}$. The effect of the spin-orbit interaction is taken into account when determining the potential-energy curves of the molecular negative ion. The vibrational excitation cross sections are compared with other available theoretical and experimental results.

Rovibrationally state-specific collision model for the O2(Σg-3) + O(P3) system in DSMC.

A rovibrationally state-specific collision model for the O2(Σg-3)+O(P3) system is presented for direct simulation Monte Carlo, including rotation-vibration-translation energy transfer, exchange, dissociation, and recombination processes. The two-step binary collision approach is employed to model recombination reactions. Two available cross section databases by Andrienko/Boyd and Esposito/Capitelli are employed for the rovibrationally resolved model (rv-STS) and vibrationally resolved model (v-STS), respectively. The difference between rv-STS and v-STS comes from two contributions: the multisurface factor of dissociation (fMS) and the rotational averaging process. The dissociation cross section with the constant fMS is typically larger than with the variable fMS, especially for the low vibrational energy states. On the other hand, the cross sections resulting from the rotationally averaged database are found to underpredict the dissociation rate coefficient at low temperatures. In the rovibrational heating case, the rv-STS predicts faster relaxation than the v-STS, which also shows a lower quasi-steady-state temperature than v-STS. In the rovibrational cooling case, the rv-STS shows a faster relaxation than v-STS, which also presents a thermal non-equilibrium between rovibrational and translational mode during the cooling process.

On the efficiency of CO2 conversion in corona and dielectric-barrier discharges

The regimes of CO2 discharges are considered in which conversion of CO2 molecules proceeds mainly due to dissociation by electron impact. The efficiency of this process is estimated in the framework of an approximate analytical approach, using various CO2 dissociation cross sections available in the literature. It is shown that the best fit with the set of experimental data of the conversion efficiency in corona and dielectric-barrier discharges, corresponding to the range of reduced electric field values higher than 90 Td, is provided by using, as the dissociation cross section, of the cross section by Phelps, for excitation of electronic states with the energy threshold of 10.5 eV.

Isotopic and vibrational-level dependence of H2 dissociation by electron impact

The low-energy electron-impact dissociation of molecular hydrogen has been a source of disagreement between various calculations and measurements for decades. Excitation of the ground state of H$_2$ into the dissociative $b ^3\Sigma_u^+$ state is now well understood, with the most recent measurements being in excellent agreement with the molecular convergent close-coupling (MCCC) calculations of both integral and differential cross sections (2018 Phys. Rev. A 98 062704). However, in the absence of similar measurements for vibrationally-excited or isotopically-substituted H$_2$, cross sections for dissociation of these species must be determined by theory alone. We have identified large discrepancies between MCCC calculations and the recommended $R$-matrix cross sections for dissociation of vibrationally-excited H$_2$, D$_2$, T$_2$, HD, HT, and DT (2002 Plasma Phys. Contr. F. 44 1263-1276,2217-2230), with disagreement in both the isotope effect and dependence on initial vibrational level. Here we investigate the source of the discrepancies, and discuss the consequences for plasma models which have incorporated the previously recommended data.

Dynamics of diffractive dissociation

We describe a QCD based model which incorporates the main properties of the inclusive particle distributions expected for diffractive processes, including the diffractive dissociation at high energies. We study, in turn, the total cross section, sigma _mathrm{tot}, the differential elastic, dsigma _mathrm{el}/dt, cross section, the dependence of the single proton dissociation cross section, xi dsigma ^mathrm{SD}/dxi , on the momentum fraction, xi =1-x_L, lost by the leading proton, the multiplicity distributions in inelastic (non-diffractive) collisions and in the processes of dissociation. Besides this we calculate the mean transverse momenta of the ‘wee partons’ (secondaries) produced in the case of dissociation (that is in the processes with a large rapidity gap) and compare it with that in inelastic interactions.

Dynamical simulation of collision-induced dissociation of pyrene dimer cation

We report a theoretical investigation of the collision-induced dissociation of pyrene dimer cation, as recently investigated in the experimental work by Zamith et al. (J. Chem. Phys. 153, 054311 (2020)). Molecular dynamics simulations using potential energies and forces computed at the self-consistent charge density functional-based tight binding level were conducted for different collision energies between 2.5 and 30 eV. It appears that most of the dissociation occurs on a short timescale (less than 3 ps). The dynamical simulations allow to visualize the dissociation processes. At low collision energies, the dissociation cross section increases with collision energies, whereas it remains almost constant for collision energies greater than 10-15 eV. The analysis of the kinetic energy partition is used to get insights into the collision/dissociation processes at the atomic scale. The simulated time-of-flight mass spectra of parent and dissociation products are obtained from the combination of molecular dynamics simulations and phase space theory to address the short and long timescales dissociation, respectively. The agreement between the simulated and measured mass spectra suggests that the main processes are captured by this approach.

Взаимодействие низкоэнергетических электронов с молекулами D-рибозы

Abstract– The interactions of low-energy electrons (&lt;20 eV) with D-ribose molecules, namely, electron scattering and dissociative attachment, are studied. The results of these studies showed that the fragmentation of D-ribose molecules occurs effectively even at an electron energy close to zero. as well as in the energy range 5.50–9.50 eV. In the total cross section of electron scattering by molecules, resonance features at energies of 5.00–9.00 eV in the region of formation of ionic fragments C3H4O2–, C2H3O2–, OH–, associated with the destruction of molecular heterocycles, were experimentally discovered for the first time. The correlation of the features observed in the scattering and dissociative electron attachment cross sections is analyzed.

Absolute dissociative electron attachment cross-section measurement of difluoromethane

Dissociative electron attachment (DEA) and ion-pair dissociation (IPD) processes of Difluoromethane (CH$_2$F$_2$) have been studied in the incident electron energy range 0 to 45 eV. Three different fragment anions (F$^-$, CHF$^-$ and F$_2^-$) are detected in the DEA range and two anions (F$^-$ and CHF$^-$) are detected in IPD range. Absolute cross-section of the F$^-$ fragment ion is measured for the first time. Three different resonances for both F$^-$ and CHF$^-$ ions and one single resonance peak for the F$_2^-$ ions are observed. Constant increase in ion counts above 8 eV incident electron energy indicates the involvement of IPD process. From the experimental observation, it is speculated that near 11 eV incident electron energy both DEA and IPD processes occur simultaneously.

Self-consistent electron–THF cross sections derived using data-driven swarm analysis with a neural network model

We present a set of self-consistent cross sections for electron transport in gaseous tetrahydrofuran (THF), that refines the set published in our previous study [] by proposing modifications to the quasielastic momentum transfer, neutral dissociation, ionisation and electron attachment cross sections. These adjustments are made through the analysis of pulsed-Townsend swarm transport coefficients, for electron transport in pure THF and in mixtures of THF with argon. To automate this analysis, we employ a neural network model that is trained to solve this inverse swarm problem for realistic cross sections from the LXCat project. The accuracy, completeness and self-consistency of the proposed refined THF cross section set is assessed by comparing the analyzed swarm transport coefficient measurements to those simulated via the numerical solution of Boltzmann’s equation.

Dissociative electron attachment cross sections for ro-vibrationally excited NO molecule and N − anion formation

Motivated by the huge need for data for non-equilibrium plasma modeling, a theoretical investigation of dissociative electron attachment to the NO molecule is performed. The calculations presented here are based on the local-complex-potential approach, taking into account five NO− resonances. Three specific channels of the process are studied, including the production of excited nitrogen atoms N(2D) and of its anions N−. Interpretation of the existing experimental data and their comparison with our theoretical result are given. A full set of ro-vibrationally-resolved cross sections and the corresponding rate coefficients are reported. In particular, a relatively large cross sections for N− ion formation at low energy of the incident electron and for vibrationally excited NO target are predicted. Finally, molecular rotation effects are discussed.

Radiolysis of NH3:CO ice mixtures – implications for Solar system and interstellar ices

ABSTRACT Experimental results on the processing of NH3:CO ice mixtures of astrophysical relevance by energetic (538 MeV 64Ni24+) projectiles are presented. NH3 and CO are two molecules relatively common in interstellar medium and Solar system; they may be precursors of amino acids. 64Ni ions may be considered as representative of heavy cosmic ray analogues. Laboratory data were collected using mid-infrared Fourier transform spectroscopy and revealed the formation of ammonium cation (NH$_4^+$), cyanate (OCN−), molecular nitrogen (N2), and CO2. Tentative assignments of carbamic acid (NH2COOH), formate ion (HCOO−), zwitterionic glycine (NH$_3^+$CH2COO−), and ammonium carbamate (NH$_4^+$NH2COO−) are proposed. Despite the confirmation on the synthesis of several complex species bearing C, H, O, and N atoms, no N–O-bearing species was detected. Moreover, parameters relevant for computational astrophysics, such as destruction and formation cross-sections, are determined for the precursor and the main detected species. Those values scale with the electronic stopping power (Se) roughly as σ ∼ a S$_\mathrm{ e}^n$, where n ∼ 3/2. The power law is helpful for predicting the CO and NH3 dissociation and CO2 formation cross-sections for other ions and energies; these predictions allow estimating the effects of the entire cosmic ray radiation field.

Scaling Platinum-Catalyzed Hydrogen Dissociation on Corrugated Surfaces.

We determine absolute reactivities for dissociation at low coordinated Pt sites. Two curved Pt(111) single‐crystal surfaces allow us to probe either straight or highly kinked step edges with molecules impinging at a low impact energy. A model extracts the average reactivity of inner and outer kink atoms, which is compared to the reactivity of straight A‐ and B‐type steps. Local surface coordination numbers do not adequately capture reactivity trends for H2 dissociation. We utilize the increase of reactivity with step density to determine the area over which a step causes increased dissociation. This step‐type specific reactive area extends beyond the step edge onto the (111) terrace. It defines the reaction cross‐section for H2 dissociation at the step, bypassing assumptions about contributions of individual types of surface atoms. Our results stress the non‐local nature of H2 interaction with a surface and provide insight into reactivity differences for nearly identical step sites.

Parity Violation in Proton—Deuteron Scattering

The effects of parity violation in the interaction of relativistic polarized protons and deuterons are discussed. Within Glauber's approach, estimates are obtained for P-odd asymmetries in the total and elastic scattering cross sections, in the deuteron dissociation cross section, and in the inelastic cross section with meson production in a final state. It is shown that, from the point of view of the magnitude of the P-odd effects, the interaction of polarized deuterons with unpolarized protons has an advantage over the interaction of polarized protons with unpolarized deuterons. A significant P-odd asymmetry was found in the dissociation channel of the polarized deuteron.

Electron Scattering Cross Sections for Anthracene and Pyrene.

UK molecular R-matrix calculations have been carried out for electron scattering from anthracene and pyrene. These molecules belong to the family of polycyclic hydrocarbons (PAHs) and are found in a nebula known as the Red Rectangle. Static exchange (SE), static exchange plus polarization (SEP), and close coupling (CC) approximations are used for scattering calculations. Different elastic and inelastic cross sections are computed in the present work in the energy range of 0.1-15 eV. Dissociative electron attachment cross sections are also calculated for both the molecules. Various shape, Feshbach/core-excited, and mixed resonances are detected for these molecules below 10 eV. All of the resonances detected in the present study are in agreement with the existing experimental and theoretical results. Due to the complexity of the present targets, electron collision cross sections are essentially unknown and hence most of the results are presented for the first time.