Reactive Collisions Research Articles

Gas-phase Formation of Large, Astronomically Relevant Polycyclic Aromatic Hydrocarbon Clusters

As one class of important carbon reservoirs in interstellar clouds, large polycyclic aromatic hydrocarbons (PAHs) and their derivative species play an important role in the formation and evolution of interstellar carbonaceous compounds. To understand these chemical routes, the gas-phase ion–molecular collision reaction between large, astronomically relevant PAH (dicoronylene, DC, C48H20) cations and smaller neutral superhydrogenated PAHs (2, 3–benzofluorene, C17H12) are investigated. Series of large DC/2, 3–benzofluorene cluster cations (e.g., [(C17H12)6C48H14]+, 236 atoms, and [(C17H12)5C48]+, 193 atoms) are efficiently formed by gas-phase condensation under laser irradiation conditions. With theoretical calculations, the structure of newly formed DC/2, 3-benzofluorene cluster cations and the bonding energy for these formation reactions are obtained. Moreover, the IR spectra of DC/2, 3-benzofluorene cluster cations are also calculated. The gas-phase reactions between large PAH species occur relatively easily, resulting in a very large number of reactions and very complex molecular clusters. The adduct processes and the formed molecular structure relatively depend on the carbon reaction sites. The carbon edge sites have different chemical reactivity, which may affect the abundance of these relevant interstellar substances. Furthermore, intermolecular hydrogen transfer plays an important role in cluster formation processes, which can lead the newly formed clusters to become more stable. We infer that small superhydrogenated PAH molecules (e.g., 2, 3-benzofluorene) can effectively aggregate on the large PAH molecules (e.g., dehydrogenated DC cations or carbon clusters) in the gas phase, which provides proposed chemical-evolution routes (ion–molecular reaction pathways) for the formation of the nanometer-sized dust grains in a bottom-up process (in building block pathways) in the interstellar medium.

Cross-Sections for Projectile Ionization, Electron Capture, and System Breakdown of C5+ and Li2+ Ions with Atomic Hydrogen

For many disciplines of science, all conceivable collisional cross-sections and reactions must be precisely known. Although recent decades have seen a trial of large-scale research to obtain such data, many essential atomic and molecular cross-section data are still missing, and the reliability of the existing cross-sections has to be validated. In this paper, we present projectile ionization, electron capture, and system breakdown cross-sections in carbon (C5+) ions and lithium (Li2+) ion collisions with atomic hydrogen based on the Monte Carlo models of classical and quasi-classical trajectories. According to our expectation, the QCTMC results show higher results in comparison to standard CTMC data, emphasizing the role of the Heisenberg correction constraint, especially in the low-energy regime. On the other hand, at high energy, the Heisenberg correction term has less influence as the projectile momentum increases. We present the total cross-sections of projectile ionization, electron capture, and system breakdown in C5+ ions and Li2+ ion collisions with atomic hydrogen in the impact energy range from 10 keV to 160 keV, which is of interest in astrophysical plasmas, atmospheric sciences, plasma laboratories, and fusion research.

Rate coefficients for C and O2 reactive collisions relevant to interstellar clouds from QCT and machine learning.

The chemical reactions between certain interstellar molecules are exothermic in nature and barrierless in the entrance channel, allowing these reactions to occur rapidly even at low astronomical temperatures, e.g., C and O2 interaction. Obtaining detailed rovibrational transition parameters for the reaction between C and O2, such as state-selected rate coefficients, is crucial for studying the associated atmospheric and astronomical environments. Hence, this work presents an approach that combines quasi-classical trajectory calculations with machine learning techniques based on Neural Network (NN) and Gaussian Process Regression (GPR) to determine state-selected rate coefficients. Employing this approach, we significantly reduced the computational requirements while simultaneously obtaining the accurate state-selected reaction cross sections and rate coefficients for the collision of C and O2. Both the NN-based and GPR-based models established in this work accurately predict the results calculated from explicit numerical calculations in the explored temperature range of 50-1500K, achieving a coefficient of determination R2 > 0.96. Most importantly, the current work provides the most comprehensive dataset of rovibrational rate coefficients of v = 0-4, j = 0-70 → v' = 0-15 for the astrophysical modeling of the C-O2 collision system.

A global model and two-dimensional simulation study of a low-pressure inductively coupled CF4 plasma considering non-Maxwellian EEDF

We analyze the discharge characteristics of a low-pressure inductively coupled CF4 plasma using a global model and a two-dimensional (2D) simulation. We first conducted a study comparing the experimental results with the global model, which makes it easier to compare the trend concerning external parameters and less computationally expensive, to validate the chemical reaction data, and then, compared the experimental results with the 2D simulation results. We then analyzed the discharge characteristics by comparing the 2D model results with the global model at various gas pressures and powers. The simulations were performed using COMSOL software, which is based on a fluid model. The electron energy distribution function (EEDF) was solved self-consistently using the Boltzmann equation solver, and then, coupled with the fluid model. The results were more consistent with the experimental results when the EEDF was calculated by solving the Boltzmann equation than for assuming the Maxwellian EEDF. Furthermore, the global model results were similar with the mean values obtained from the 2D model. This indicates that it is efficient to first validate the electron collision cross sections and reaction coefficients using the global model. Our approach is expected to be utilized in the analysis of new gases.

Atmospheric pressure plasma jet interacting with a droplet on dielectric surface

Abstract The chemical processes at plasma–liquid interface has become a crucial point for plasmas’ various applications. In this study, the interaction between atmospheric pressure plasma jet and different-scale droplets were investigated by both experiments and modeling. The interaction transited from ‘annular’ mode to ‘solid’ mode when plasma involved with different size of droplets. As the droplet size increased, the high-field region moved from the plasma jet head to the gap between plasma jet head and droplet vertex surface. Additionally, the time averaged surface fluxes of the main active species were analyzed. For the flux of singlet oxygen (1O2), both small and medium-scale droplets reached the maximum value in the central region of the droplets, while for large-scale droplet, the maximum value was observed in the edge region of the droplet. This was due to the fact that, compared to small and medium-scale droplet, the edges of large-scale droplet are closer to the He–Air mixed boundary layer, where more oxygen molecules were provided in the gas environment, leading to enhanced electron collision reactions with oxygen molecules. The cause for these behaviors were also analyzed and discussed. This work shed light on the interaction mechanism for plasma–liquid interactions, which provides significant guidance for plasma medical or water treatment applications.

Effects of anode evaporation process on the anode sheath characteristics in vacuum arc plasma

Abstract The anode sheath of vacuum arc plasma plays a key role in the generation of anode plasma, but the effects of anode evaporation on the anode sheath remains unclear. In this paper, a theoretical model of a collisional sheath for multi-component plasma coupled with anode evaporation is developed, and the spatial evolution of the anode sheath at different anode surface temperatures is investigated. The results indicate that the distribution of charged particles density and potential in the anode sheath monotonically decreases in the absence or reduction of anode evaporation. When the anode surface temperature exceeds 1900K, a potential hump appears within the sheath. This is due to enhanced anode evaporation increasing the metal vapor density, which intensifies electron impact ionization and charge exchange collisions, resulting in a higher net space charge density. Finally, the effects of various collision reactions and electron temperatures on the potential hump are analyzed. These findings are meaningful for understanding the anode plasma generation mechanism and regulating the anode plasma parameters.

Nuclear Quantum Effects on the Nature of Hydroboration Selectivity: Experimental Effects of First-Collision Tunneling.

The understanding of selectivity in reactions exhibiting nonstatistical dynamics is impeded by the limitations of trajectory studies with regard to nuclear quantum effects, especially tunneling. We described here the use of ring-polymer molecular dynamics (RPMD) to account for an unusual regiochemical isotope effect on the regioselectivity of hydroborations of alkenes with BH3/BD3. RPMD is able to account for the experimental observation, while statistical approaches and classical trajectories fail. The combination of experiment and RPMD trajectories suggests that tunneling in the initial collision of reactants is the major source of the nonstatistical selectivity.

Electrochemical Investigation of Plasma Channels During Hydraulic‐Electric Pulsed Discharges

ABSTRACTThe hydraulic‐electric pulsed discharge(HEPD) rock‐breaking technology is a new high‐efficiency technology that generates plasma shock waves to rupture rocks. Since the plasma channel formation mechanism involved in HEPD rock‐breaking technology is difficult to describe, there are fewer theoretical models of this technology. This paper establishes a HEPD plasma model, which integrally considers the mutual coupling between five physical fields. The multi‐physical field model realizes the whole process of plasma channels, breakdown channels, plasma shock waves, and plasma shock wave rock‐breaking during the HEPD. The changes in mass fraction, density, and diffusion flux of relevant elements in the electrochemical reaction equation of the plasma channel are comprehensively analyzed. The obtained plasma multiphysics field model shows that the interpenetration of charged ions forms the breakdown channel and plasma channel. The anion number density is related to the H‐ number density, and the decrease in H‐ number density is due to the fact that the energy in the plasma channel is not sufficient to satisfy the relevant chemical equations to continue the collision reaction. The damage to the rock by the plasma shock wave takes the form of a gradual spreading of the plasma shock wave from the center of the rock to the edges, which leads to rock fragmentation. The model has the potential to establish a link between HEPD rock‐breaking parameters and the efficiency of HEPD rock‐breaking, which could provide a practical way for the development and parameter optimization of hydraulic‐electric pulsed discharge rock‐breaking tools.

Simulation on the hollow cathode discharge in hydrogen

A rectangular hollow cathode discharge (HCD) in hydrogen with a pressure of 2 Torr is simulated using a 2-D fluid model. The potential, electric field, particle density, and average electron temperature are calculated. The discharge space consists of the cathode sheath region near the cathode electrode and the negative glow (NG) region in the central region of the discharge cell. A high electric field of thousands of V/cm and a low electric field of tens of V/cm appear in the cathode sheath region and NG region, respectively. The average electron temperature in the cathode sheath region is tens of eV, which is significantly higher than that in the NG region. Electrons and H3 + are the main negative particles and positive ions, whose peaks appear in the NG region, and the peak magnitude is on the order of 1010 cm−3. H atom is the highest-density neutral particle other than H2 with a peak density of 1013 cm−3. The reaction kinetics of the generation and consumption of different particles are explored. The results show that each reaction generates certain particles while consuming other particles, ultimately achieving a dynamic equilibrium in the density of various particles. The electrons mainly originate from the ground state ionization between electron and H2 (e+H2 → e+H2 ++e) and are consumed by the dissociative attachment (e+H2 → H−+H). The charge transfer collision reaction (H2 ++H2 → H3 ++H) is the only reaction that produces H3 + ions. Different reactions to the consumption of H3 + ions do not differ significantly. The generation and consumption of H mainly originate from the electron collision dissociation reaction (e+H2 → e+H+H) and the ionization reaction (e+H→H++2e).

Intracluster reaction dynamics of NO+(H2O)n.

Nitric oxide (NO) and NO-water clusters play crucial roles in the D-region of the atmosphere because it is postulated that NO+ reacts with H2O to produce nitrous acid (HONO) and H3O+. HONO is the major precursor of the hydroxyl radicals leading to the formation of secondary pollutants. The sources of atmospheric HONO, however, are not fully understood. Previously, the sequential H2O addition reaction, H2O + NO+(H2O)n, and the bi-molecular collision reaction, NO+ + (H2O)n, have been investigated by both experiments and theoretical calculations to determine the formation mechanism of HONO. However, the photo-reactions from NO(H2O)n neutral clusters were not considered for the formation mechanism of HONO. In this study, the intra-cluster reactions of NO+(H2O)n clusters, following ionization of the parent neutral cluster of NO(H2O)n, were investigated using the direct abinitio molecular dynamics method. When n = 4, [NO+(H2O)4]ver [vertical ionization state of NO(H2O)n] yielded HONO and hydrated H3O+ after the intra-cluster reaction, and the reaction time was calculated to be 150fs. The reaction is expressed as [NO+(H2O)n]ver → HONO + H3O+(H2O)n-2 (reactive) (n > 3). Larger clusters of [NO+(H2O)n]ver (n = 5-8) also yield HONO. In contrast, in smaller clusters (n = 1-3), only solvent re-orientation around NO+ occurred after the ionization: [NO+(H2O)n]ver → NO+(H2O)n (solvent re-orientation) (n = 1-3). The hydration energy of H3O+, which depends on the cluster size (n), plays an important role in promoting the formation of HONO. The reaction mechanism is discussed based on theoretical results.

Plasma simulation of HF plasma generated in dual-frequency chamber for high aspect ratio dielectric etching

For the 3D NAND memory hole with a high aspect ratio above 100, the etching process with hydrogen-fluoride (HF) contained plasmas has been proposed. We have developed a simulation model for gas-phase reactions that reproduces the HF plasma in experiments. The HF plasma was generated using a power supply of 100 MHz frequency, and electron and F densities were measured. The simulation model was constructed on the basis of the collision cross sections and reaction constants reported in the previous papers, and the F density in the simulation was calibrated by comparing it with that in the experiments. As a result of the plasma simulation, the densities of F and the electrons were determined to be 7.52 × 1016 m–3 and 8.50 × 1016 m–3, respectively. Taking into consideration the errors in the experiment, we considered that the simulation model is able to reproduce the experimental HF plasma well.

On the use of reactive multiparticle collision dynamics to gather particulate level information from simulations of epidemic models

This paper discusses the application of reactive multiparticle collision (RMPC) dynamics, a particle-based method, to epidemic models. First, we consider a susceptible-infectious-recovered framework to obtain data on contacts of susceptibles with infectious people in a population. It is found that the number of contacts increases and the contact duration decreases with increases in the disease transmission rate and average population speed. Next, we obtain reinfection statistics for a general infectious disease from RMPC simulations of a susceptible-infectious-recovered-susceptible model. Finally, we simulate a susceptible-exposed-infectious-recovered model and gather the exposure, infection, and recovery time for the individuals in the population under consideration. It is worth mentioning that we can collect data in the form of average contact duration, average initial infection time, etc., from RMPC simulations of these models, which is not possible with population-based stochastic models, or deterministic systems. This study provides quantitative insights on the potential of RMPC to simulate epidemic models and motivates future efforts for its application in the field of mathematical epidemiology.

Influence of Singlet Oxygen in H + O2 Collision Reaction.

The collision reaction of H + O2 = OH + O is a pivotal step in combustion. To investigate the influence of singlet oxygen on this reaction, we computed potential energy surfaces (PESs) for all six lowest states using high-level ab initio methods and coupled them with embedded atom neural network (EANN) fitting. By integrating quasi-classical trajectory (QCT) with trajectory surface hopping (TSH) based on the fitted PESs, we simulated the dynamics of both ground- and excited-states to derive the reaction rate constants for the forward and reverse processes. The results reveal that the forward reaction facilitates radical generation, promoting combustion reactions. Furthermore, calculations of reverse reaction rate constants indicate that all electronic states ultimately yield ground-state oxygen, leading to radical deactivation and exerting an inhibitory effect on combustion processes.

Magnetic field and dielectric beads modulate DBD reduced electric field with discharge homogeneity to realize NOx differential conversion

In this paper, the reduced electric field and the discharge homogeneity of DBD were modulated by the magnetic field and the packed ZrO2 beads. Subsequently, the reduced electric field and the discharge homogeneity on discharge performance, de-NOx efficiency and NOx conversion mechanism were evaluated. The experimental results show that the reduced electric field gradually enhances as the magnetic field increases, promoting de-NOx performance. The discharge homogeneity significantly weakens with the length of packed ZrO2 beads increases, inhibiting the de-NOx performance. Compared to the reactor with the packed ZrO2 beads, the de-NOx efficiency of the reactor with a 0.2 T magnetic field can achieve 87.2 %, an improvement of 39.3 %. Meanwhile, the selectivity of NO2 and N2O are reduced by 18.3 % and 21 %, respectively. The de-NOx mechanisms indicate that the reduced electric field affects the electron collision reactions and the relative rate of the NOx conversion reactions by altering the electron energy distribution. The discharge homogeneity alters the degree of plasma mitigation of exhaust gases by regulating the absolute rate of the NOx conversion reactions. The by-product N2O is mainly dependent on the concentration of NO2 and is less sensitive to N2(A3). This work reveals the differential mechanisms of reduced electric field and discharge homogeneity on de-NOx.

Nonadiabatic Molecular Dynamics with Fermionic Subspace-Expansion Algorithms on Quantum Computers.

We introduce a novel computational framework for excited-state molecular quantum dynamics simulations driven by quantum-computing-based electronic-structure calculations. This framework leverages the fewest-switches surface-hopping method for simulating the nuclear dynamics and calculates the required excited-state transition properties with different flavors of the quantum subspace expansion and quantum equation-of-motion algorithms. We apply our method to simulate the collision reaction between a hydrogen atom and a hydrogen molecule. For this system, we critically compare the accuracy and efficiency of different quantum subspace expansion and equation-of-motion algorithms and show that only methods that can capture both weak and strong electron correlation effects can properly describe the nonadiabatic effects that tune the reactive event.

The role of intersystem crossing in the reactive collision of S+(4S) with H2.

We report a study on the reactive collision of S+(4S) with H2, HD, and D2 combining guided ion beam experiments and quantum-mechanical calculations. It is found that the reactive cross sections reflect the existence of two different mechanisms, one being spin-forbidden. Using different models, we demonstrate that the spin-forbidden pathway follows a complex mechanism involving three electronic states instead of two as previously thought. The good agreement between theory and experiment validates the methodology employed and allows us to fully understand the reaction mechanism. This study also provides new fundamental insights into the intersystem crossing process.

MOB-Net: Limb-modularized uncertainty torque learning of humanoids for sensorless external torque estimation

Momentum observer (MOB) can estimate external joint torque without requiring additional sensors, such as force/torque or joint torque sensors. However, the estimation performance of MOB deteriorates due to the model uncertainty which encompasses the modeling errors and the joint friction. Moreover, the estimation error is significant when MOB is applied to high-dimensional floating-base humanoids, which prevents the estimated external joint torque from being used for force control or collision detection in the real humanoid robot. In this paper, the pure external joint torque estimation method named MOB-Net, is proposed for humanoids. MOB-Net learns the model uncertainty torque and calibrates the estimated signal of MOB, substantially reducing the estimation errors of MOB. The external joint torque can be estimated in the generalized coordinate including whole-body and virtual joints of the floating-base robot with only internal sensors (an IMU on the pelvis and encoders in the joints). Furthermore, MOB-Net shows more robust performance for the unseen data compared to the end-to-end learning method, and the robustness of MOB-Net is validated through extensive simulations, real robot experiments, and ablation studies. Finally, various collision handling scenarios are presented to show the versatility of MOB-Net: contact wrench feedback control for locomotion, collision detection, and collision reaction for safety.

Extension of ion-neutral reactive collision model DNT+ to polar molecules based on average dipole orientation theory

The ion-neutral reactive collision model DNT+, which generates comprehensive ion-neutral collision cross section (CS) data sets for atoms and nonpolar molecules, has been extended to polar molecules. The extension is based on the average dipole orientation (ADO) theory, which adds the dipole moment to Langevin–Hassé CS. Furthermore, the ADO CS for short-range reactive collisions is covered with a rigid core to incorporate long-range elastic and charge-exchange collisions. The modified version of DNT+, i.e., DNT+DM, is applied to gas-phase H2O+–H2O and low-energy CF3+–CO collisions for its validation. The cross sections (CSs) for those collisions using DNT+DM show good agreement with literature data, proving that DNT+DM is valid to some extent. Help with ion swarm analyses and measurements is needed to make the predicted CSs more accurate.

Breaking scaling relation of single-atom site via energy storage-release effect from adjacent carbon vacancy for low-temperature-resistant Fenton-like catalysis

To realize efficient antibiotics degradation in low-temperature water, single-atom FeN4 sites are engineered near carbon vacancies in a porous catalyst (PCvFe1-5) via thermal-etching and pyrolysis. The high-specific-surface-area (2202.80 m2 g−1) carbon support and dispersive Fe atoms co-enrich sulfamethoxazole and peroxymonosulfate to enhance the reactant collision frequency. Carbon vacancies allow the catalyst to deform for storing the peroxymonosulfate adsorption energies at FeN4 sites, which are subsequently released to facilitate -SO4H desorption for rapid site regeneration. This breaks the scaling relation suffered by single-atom sites, thereby reducing the thermodynamic energy barrier. Consequently, a low-temperature-resistant Fenton-like system with ultralow activation energy of 9.06 kJ mol−1 is constructed for sulfamethoxazole degradation. The normalized kinetic rate constant at 2 ℃ exceeds that of reported catalysts working at 25/30 ℃ by 1–2 orders of magnitude. Moreover, due to the special site configuration, PCvFe1-5 degrades sulfamethoxazole via both long-range catalyst-mediated electron transfer and short-range direct collision oxidation.

Gas-phase hydrogenation processes of cationic carbon clusters

ABSTRACT In this work, the gas-phase ion–atom collision reaction between large cationic carbon clusters and H-atoms is investigated. The carbon cluster cations (C$_{48-2*n}$$^+$, n = [0$-$8]) are produced from the photo-fragmentation processes of large PAH (dicoronylene, DC, C$_{48}$H$_{20}$) cations. The hydrogenated carbon cluster cations are efficiently formed (e.g. C$_{44/46}$H$_{9}$$^+$), and no even–odd hydrogenated mass patterns are observed. The hydrogenation behaviour and hydrogenation rate for these carbon cluster cations are the same. With theoretical calculations, the formation and bending processes of carbon cluster cations, the structure of these newly formed hydrogenated carbon cluster cations, and the bonding energies for the hydrogenation pathways are investigated. During the formation process of carbon clusters, the zigzagged edges gradually increase, and the planar configuration tends towards a bent and folded molecular configuration, i.e. from graphene to fullerene structures. The bending process with higher exothermic energies provides a reasonable explanation for the formation of the ‘magic numbers’ (e.g. C-atoms = 44) carbon clusters and their greater stability. The exothermic energy for each hydrogenation reaction pathway is relatively high; consequently, the forms and the hydrogenated states of carbon clusters are complex. The hydrogenation ability of edge carbon sites is higher than that of internal carbon sites; after bending and folding, the hydrogenation ability of these originally internal carbon sites becomes higher due to structural caged. As a result, under the co-evolution interstellar chemistry network, the (hydrogenation) states and forms of carbon compounds are complicated and diverse in the ISM.