Collisional Energy Transfer Research Articles

StaR-LIF: State-resolved laser-induced fluorescence modeling for diatomic molecules

This study introduced a new model for quantitative analysis of the state-resolved laser-induced fluorescence signal of diatomic molecules, namely StaR-LIF. This model is built upon a master equation of the collisional-radiative transfer processes, which incorporated the latest data on the collisional energy transfer rates between individual spin- and parity-resolved rovibronic quantum levels, together with the most recent updates on the energy levels, line strengths and broadening/shift parameters of the relevant absorption and fluorescence transitions. To facilitate the use of this model, a web-based graphic user interface has been developed and made available at https://starlif.pku.edu.cn. Example applications of the current model have been demonstrated for NO, OH and CH, including parametric studies on the effects of variable pulse width and saturating excitation, as well as the temporal evolution of fluorescence spectrum during collisional transfer. The StaR-LIF model can provide quantitative modeling and analysis capabilities over a wide range of gasdynamic and excitation conditions, and promises to be useful in future LIF studies of complex reacting flows.

Frustrated charge transfer in vibrationally inelastic Ar++N2 collisions via hard collision glory scattering

Vibrational energy transfer in collisions between ions and neutrals is a fundamental process in interstellar media, planetary atmospheres, and plasmas. The conventional wisdom is that glancing collisions with large impact parameters are forward-scattered with low vibrational excitation, while hard collisions with small impact parameters are sideway- or backward-scattered with relatively high vibrational excitation. Here, we report experimental observations with a three-dimensional velocity-map imaging crossed-beam apparatus in the inelastic scattering process Ar++N2(v′′ = 0, J′′)→Ar++N2(v′, J′), where all the vibrationally excited N2 products are dominated by forward scattering, contradicting the textbook model. Trajectory surface hopping calculations not only reproduced the experimental observation qualitatively, but also revealed that the vibrational excitation mainly occurs through a transient charge-transfer process. The hard collision glory mechanism, which has so far only been observed in inelastic rotational energy transfer between neutrals, is shown to play a major role for vibrational excitation in the inelastic Ar++N2 collision, via the frustrated charge transfer process.

Quantitative time-resolved diagnostics of electric field dynamics during individual plasma breakdown events using burst laser pulse electric field induced second harmonic generation

In plasma discharges, the acceleration of electrons by a fast varying electric field and the subsequent collisional electron energy transfer determines the plasma dynamics, chemical reactivity, and breakdown. Current in situ electric field measurements require reconstruction of the temporal profile over many observations. However, such methods are unsuitable for non-repetitive and unstable plasmas. Here, we present a method for creating “movies” of dynamic electric fields in a single acquisition at sample rates of 500 × 106 fps. This ultrafast diagnostic was demonstrated in radio frequency electric fields between two parallel plates in air, as well as in Ar nanosecond-pulsed single-sided dielectric barrier discharges.

Secondary scintillation yield from GEM electron avalanches in - and --isobutane for CYGNO — Directional Dark Matter search with an optical TPC

CYGNO is an international collaboration with the aim of operating a ▪ optical time projection chamber (TPC) for directional Dark Matter (DM) searches and solar neutrino spectroscopy, to be deployed at the Laboratori Nazionali del Gran Sasso (LNGS). A ▪/▪ (60/40) mixture is used, along with a triple Gas Electron Multiplier (GEM) cascade to amplify the ionisation signal. The scintillation produced in the electron avalanches is read out using a scientific complementary metal–oxide–semiconductor (sCMOS) camera. This solution has proven to provide very high sensitivity to interactions in the few ▪ energy range. The inclusion of a hydrogen-based gas will offer an even lighter target, resulting in a more efficient energy transfer in a DM particle collision, and consequently, a lower detection threshold. Additionally, longer track lengths of light nuclear recoils are easier to detect with a clearer direction. However, the addition of such gas will contribute to quenching the scintillation, jeopardizing the TPC performance. In this work, we demonstrate the feasibility of adding 1% to 5% isobutane to the ▪/▪ (60/40) mixture by measuring the respective absolute scintillation yield output. The overall scintillation produced in the charge avalanches is not drastically suppressed by quenching due to the isobutane addition. The presence of Penning transfer from excited He atoms to isobutane molecules increases the number of electrons in the avalanches, partially compensating for the loss of scintillation due to quenching. For the highest applied GEM voltage, the total number of photons produced in the avalanche per ▪ deposited in the absorption region presents a decrease of only a factor of about three, from 2.30(20)×104 to 8.2(4)×103▪, as the isobutane content increases from 0 to 5%. The quantification of the visible component of the scintillation shows that isobutane quenches both visible and ultraviolet (UV) photons emitted by ▪/▪.

Dynamics of the HCl + C2H5 Multichannel Reaction on a Full-Dimensional Ab Initio Potential Energy Surface.

We report a full-dimensional ab initio analytical potential energy surface (PES), which accurately describes the HCl + C2H5 multichannel reaction. The new PES is developed by iteratively adding selected configurations along HCl + C2H5 quasi-classical trajectories (QCTs), thereby improving our previous Cl(2P3/2) + C2H6 PES using the Robosurfer program package. QCT simulations for the H'Cl + C2H5 reaction reveal hydrogen-abstraction, chlorine-abstraction, and hydrogen-exchange channels leading to Cl + C2H5H', H' + C2H5Cl, and HCl + C2H4H', respectively. Hydrogen abstraction dominates in the collision energy (Ecoll) range of 1-80 kcal/mol and proceeds with indirect isotropic scattering at low Ecoll and forward-scattered direct stripping at high Ecoll. Chlorine abstraction opens around 40 kcal/mol collision energy and becomes competitive with hydrogen abstraction at Ecoll = 80 kcal/mol. A restricted opening of the cone of acceptance in the Cl-abstraction reaction is found to result in the preference for a backward-scattering direct-rebound mechanism at all energies studied. Initial attack-angle distributions show mainly side-on collision preference of C2H5 for both abstraction reactions, and in the case of the HCl reactant, H/Cl-side preference for the H/Cl abstraction. For hydrogen abstraction, the collision energy transfer into the product translational and internal energy is almost equally significant, whereas in the case of chlorine abstraction, most of the available energy goes into the internal degrees of freedom. Hydrogen exchange is a minor channel with nearly constant reactivity in the Ecoll range of 10-80 kcal/mol.

Semiclassical analytic theory of electronic energy transfer in 3D atomic collisions.

A previously developed semiclassical theory of nonadiabatic energy transfer is used to analyze electronic excitation and quenching in three-dimensional atomic collisions. The predicted transition probabilities, cross sections, and rate coefficients are compared with the quantum scattering calculations for O + O and N + N, for the same interaction potentials and nonadiabatic coupling, and with the experimental data where available. The theory predictions are in very good agreement with quantum scattering, at the conditions when the energy transfer is dominated by a single pair of adiabatic potentials. Closed-form analytic expressions for the cross sections and rate coefficients are obtained, for both the strongly and weakly coupled cases. The results quantify and illustrate the effect of the interaction potentials and their coupling on the energy transfer. The analytic cross sections and rate coefficients are in good agreement with the numerical predictions. The same approach has been used to predict the rate coefficients of electronic excitation and quenching in collisions of N + O atoms. The fidelity of these predictions may be improved considerably if accurate potentials for the excited electronic states of N + O and their coupling are available. The applicability of the semiclassical theory for the prediction of the rates of heavy particle impact excitation in atom-molecule collisions is discussed.

Simulation of 1D atmospheric pressure dielectric barrier discharge in argon

This work aims at modelling an atmospheric-pressure homogeneous barrier discharge in argon, using a time-dependent 1D fluid model coupled to the electric field and plasmo-chemical kinetic equations. The model is chosen to mimic a discharge when a sinusoidal 1 kV voltage at 10 MHz is applied to the terminals. Energy and mass transfer are considered for a macroscopic fluid representation, while energy transfer in molecular collisions and chemical reactions is treated at the microscopic level. The macroscopic model is represented by a set of coupled partial differential equations. Microscopic effects are studied within a discrete model for electronic and molecular collisions in the frame of ZDPlasKin, a plasma modelling numerical tool. The BOLSIG+ solver is employed in solving the electronic Boltzmann equation. An operator splitting technique is used to separate microscopic and macroscopic models. The spatial and temporal evolution of such species and electron transport parameters are presented and discussed.

Demonstration of low-mode shape control in indirect-drive double shell implosions at the NIF

Double shell inertial confinement fusion is a concept for achieving robust thermonuclear burn that uses dense metal shells to compress deuterium-tritium (DT) fuel to fusion conditions. Double shell implosions are typically indirectly driven and involve a target that consists of a low-Z ablator, a foam layer, and a high-Z pusher surrounding the DT fuel. The goal of the campaign is to achieve a volumetric burn as radiation losses from the DT fuel are trapped by the opaque high-Z shell. The overall performance of double shell implosions relies on the efficient collisional transfer of kinetic energy between layers. The efficiency of this transfer (and therefore the overall performance of a given implosion) is degraded by the presence of low-mode asymmetries. P2 asymmetries are often observed in spatially resolved 2D radiographs of nominal double shell implosions. This work discusses three such experiments: one with an oblate P2 asymmetry, one with a prolate P2 asymmetry, and one with an approximate spherical symmetry. After performing a shape analysis of the oblate and prolate implosions to quantify asymmetries, these experimental results were compared with the results of hydrodynamic simulations for the two experiments. Differences between the experiment and simulation were then used to design an approximately spherical implosion by altering the incident laser cone fraction. Radiographs from the experiment that implemented the modified cone fraction show evidence of an implosion that is approximately spherical until bang time. This design is intended to serve as a point design for future studies that will seek to optimize various aspects of the double shell target.

Local models of two-temperature accretion disc coronae – II. Ion thermal conduction and the absence of disc evaporation

ABSTRACT We use local stratified shearing-box simulations with magnetic field-aligned thermal conduction to study an idealized model of the coupling between a cold, radiatively efficient accretion disc, and an overlying, hot, two-temperature corona. Evaporation of a cold disc by conduction from the hot corona has been proposed as a means of mediating the soft-to-hard state transitions observed in X-ray binary systems. We model the coronal plasma in our local disc patch as an MHD fluid subject to both free-streaming ion conduction and a parametrized cooling function that captures the collisional transfer of energy from hot ions to colder, rapidly cooling leptons. In all of our models, independent of the initial net vertical magnetic flux (NF) threading the disc, we find no evidence of disc evaporation. The ion heat flux into the disc is radiated away before conduction can heat the disc’s surface layers. When an initial NF is present, steady-state temperature, density, and outflow velocities in our model coronae are unaffected by conduction. Instead of facilitating disc evaporation, thermal conduction is more likely to feed the disc with plasma condensing out of the corona, particularly in flows without NF. Our work indicates that uncertainties in the amount of NF threading the disc hold far greater influence over whether or not the disc will evaporate into a radiatively inefficient accretion flow compared to thermal conduction. We speculate that a change in net flux mediates disc truncation/evaporation.

Inelastic scattering of formaldehyde on Au(111) surface.

Inelastic scattering between gas molecules and surfaces is a fundamental process that has been investigated extensively. In recent gas-surface scattering experiments [Phys. Chem. Chem. Phys. 19, 19904 (2017)] on formaldehyde scattering off the gold surface, the scattered formaldehyde molecules had a high propensity to excite twirling motion about the C-O bond. In the work presented here, we used classical dynamics simulations to understand energy transfer in formaldehyde-surface collisions and to probe the mechanism of interconversion of translational energy to rotational energy. The simulations reveal an increase in the rotational energy distribution with an increase in collision energies and a preferential rotational excitation about the C-O bond consistent with the experiments. The high propensity to excite the twirling motion was found to arise from a steering motion about the C-O bond during the scattering process governed by the minimum energy path.

Vibrational energy transfer in collisions of molecules with metal surfaces.

The Born-Oppenheimer approximation (BOA), which serves as the basis for our understanding of chemical bonding, reactivity and dynamics, is routinely violated for vibrationally inelastic scattering of molecules at metal surfaces. The title-field therefore represents a fascinating challenge to our conventional wisdom calling for new concepts that involve explicit electron dynamics occurring in concert with nuclear motion. Here, we review progress made in this field over the last decade, which has witnessed dramatic advances in experimental methods, thereby providing a much more extensive set of diverse observations than has ever before been available. We first review the experimental methods used in this field and then provide a systematic tour of the vast array of observations that are currently available. We show how these observations - taken together and without reference to computational simulations - lead us to a simple and intuitive picture of BOA failure in molecular dynamics at metal surfaces, one where electron transfer between the molecule and the metal plays a preeminent role. We also review recent progress made in the theory of electron transfer mediated BOA failure in molecule-surface interactions, describing the most important methods and their ability to reproduce experimental observation. Finally, we outline future directions for research and important unanswered questions.

Transient IR spectroscopy of optically centrifuged CO2 (R186-R282) and collision dynamics for the J = 244-282 states.

Collisions of optically centrifuged CO2 molecules with J = 244-282 (Erot = 22 800-30 300 cm-1) are investigated with high-resolution transient IR absorption spectroscopy to reveal collisional and orientational phenomena of molecules with hyper-thermal rotational energies. The optical centrifuge is a non-resonant optical excitation technique that uses ultrafast, 800 nm chirped pulses to drive molecules to extreme rotational states through sequential Raman transitions. The extent of rotational excitation is controlled by tuning the optical bandwidth of the excitation pulses. Frequencies of 30 R-branch ν3 fundamental IR probe transitions are measured for the J = 186-282 states of CO2, expanding beyond previously reported IR transitions up to J = 128. The optically centrifuged molecules have oriented angular momentum and unidirectional rotation. Polarization-sensitive transient IR absorption of individual rotational states of optically centrifuged molecules and their collision products reveals information about collisional energy transfer, relaxation kinetics, and dynamics of rotation-to-translation energy transfer. The transient IR probe also measures the extent of polarization anisotropy. Rotational energy transfer for lower energy molecules is discussed in terms of statistical models and a comparison highlights the role of increasing energy gap with J and angular momentum of the optically centrifuged molecules.

Mixed quantum/classical theory (MQCT) approach to the dynamics of molecule-molecule collisions in complex systems.

We developed a general theoretical approach and a user-ready computer code that permit study of the dynamics of collisional energy transfer and ro-vibrational energy exchange in complex molecule-molecule collisions. The method is a mixture of classical and quantum mechanics. The internal ro-vibrational motion of collision partners is treated quantum mechanically using a time-dependent Schrödinger equation that captures many quantum phenomena including state quantization and zero-point energy, propensity and selection rules for state-to-state transitions, quantum symmetry and interference phenomena. A significant numerical speed up is obtained by describing the translational motion of collision partners classically, using the Ehrenfest mean-field trajectory approach. Within this framework a family of approximate methods for collision dynamics is developed. Several benchmark studies for diatomic and triatomic molecules, such as H2O and ND3 collided with He, H2 and D2, show that the results of MQCT are in good agreement with full-quantum calculations in a broad range of energies, especially at high collision energies where they become nearly identical to the full quantum results. Numerical efficiency of the method and massive parallelism of the MQCT code permit us to embrace some of the most complicated collisional systems ever studied, such as C6H6 + He, CH3COOH + He and H2O + H2O. Application of MQCT to the collisions of chiral molecules such as CH3CHCH2O + He, and to molecule-surface collisions is also possible and will be pursued in the future.

Vibrational energy transfer in ammonia-helium collisions.

While the rotational energy transfer of ammonia by rare gas atoms and hydrogen molecules has been the focus of many studies, little is known about its vibrational relaxation, even though transitions involving the umbrella bending mode have been observed in many astrophysical environments. Here we explore the vibrational relaxation of the umbrella mode of ammonia induced by collisions with helium atoms by means of the close-coupling method on an ab initio potential energy surface. We compute cross sections up to kinetic energies of 1500 cm-1 and rate coefficients up to a temperature of 300 K for vibrational, rotational, and inversion transitions involving the lowest two vibrational states. We show that vibrational relaxation is much less efficient than rotation-inversion relaxation, although the rate coefficients for vibrational relaxation strongly increase with the temperature. We also observe important differences for vibrationally-elastic transitions within the lowest two vibrational states, i.e., for rotation-inversion transitions. These are a direct consequence of the difference in the tunnelling splitting of the lowest inversion levels.

Very Low-Pressure CID Experiments: High Energy Transfer and Fragmentation Pattern at the Single Collision Regime.

We have performed CID experiments on a triple quadrupole instrument, lowering the collision gas pressure by 50 times compared to its conventional value. The results show that at very low-collision gas pressure, single collisions dominate the spectra. Indirectly, these results suggest that under conventional conditions, 20-50 collisions may be typical in CID experiments. The results show a marked difference between low- and high-pressure CID spectra, the latter being characterized in terms of 'slow heating' and predominance of consecutive reactions. The results indicate that under single collision conditions, the collisional energy transfer efficiency is very high: nearly 100% of the center of mass kinetic energy is converted to internal energy.

Robustness of Threshold Collision-Induced Dissociation Simulations for Bond Dissociation Energies.

The threshold collision-induced dissociation (T-CID) method is the workhorse for gas-phase bond dissociation energy (BDE) measurements. However, T-CID does not measure BDEs directly; instead, BDEs are obtained by fitting simulated data to the experimental data. We previously observed several large discrepancies between the computed and experimental BDEs. To analyze the reliability of the experimental values, we previously reported a study of the dissociation rate models in the simulation. Here, we report a study of the collision simulation part, specifically in the L-CID (ligand CID) program. We show that the BDE values are robust even to intentionally introduced mistakes in the simulations, varying in most cases by less than 3 kcal mol-1. The most significant exception is the collisional energy transfer (CET) simulation, which led to deviations larger than 10 kcal mol-1. However, we found that the BDEs obtained with explicitly simulated CET distributions deviated by only 3 kcal mol-1 from those simulated with the original model. Collectively, our results suggest that the T-CID-derived BDE values are robust and are likely to be accurate.

Local models of two-temperature accretion disc coronae – I. Structure, outflows, and energetics

ABSTRACT We use local stratified shearing-box simulations to elucidate the impact of two-temperature thermodynamics on the thermal structure of coronae in radiatively efficient accretion flows. Rather than treating the coronal plasma as an isothermal fluid, we use a simple, parametrized cooling function that models the collisional transfer of energy from the ions to the rapidly cooling leptons. Two-temperature models naturally form temperature inversions, with a hot, magnetically dominated corona surrounding a cold disc. Simulations with net vertical flux (NF) magnetic fields launch powerful magnetocentrifugal winds that would enhance accretion in a global system. The outflow rates are much better converged with increasing box height than analogous isothermal simulations, suggesting that the winds into two-temperature coronae may be sufficiently strong to evaporate a thin disc and form a radiatively inefficient accretion flow under some conditions. We find evidence for multiphase structure in the corona, with broad density and temperature distributions, and we propose criteria for the formation of a multiphase corona. The fraction of cooling in the surface layers of the disc is substantially larger for NF fields compared to zero net-flux configurations, with moderate NF simulations radiating ≳30 per cent of the flow’s total luminosity above two mid-plane scale heights. Our work shows that NF fields may efficiently power the coronae of luminous Seyfert galaxies and quasars, providing compelling motivation for future studies of the heating mechanisms available to NF fields and the interplay of radiation with two-temperature thermodynamics.

Research on vehicle aggressiveness evaluation based on full frontal crash test

In the frontal accident, vehicles with strong aggressiveness are an important factor in causing death or injury to vulnerable vehicles. To effectively evaluate the aggressiveness of vehicle frontal crash, the dynamic load values and distribution of vehicle frontal structures are collected using the load-cell wall. On this basis, evaluation intervals in the horizontal and vertical directions are established, and the standard deviation and negative deviation of collision loads were analyzed. Normalization is carried out to establish evaluation indices for horizontal and vertical load effects. The effectiveness of the evaluation indexes is verified through analysis of frontal collision tests on several vehicle models. The results showed that the vertical and horizontal collision energy transfer at the front end of the vehicle still needs to be strengthened.

Rotational energy transfer in the collision of N2O with He atom.

The quantum state-to-state rotationally inelastic quenching of N2O by colliding with a He atom is studied on an abinitio potential energy surface with N2O lying on its vibrational ground state. The cross sections for collision energies from 10-6-100cm-1 and rate constants from 10-5-10K are calculated employing the fully converged quantum close-coupling method for the quenching of the j = 1-6 rotational states of N2O. Numerous van der Waals shapes or Feshbach resonances are observed; the cross sections of different channels are found to follow the Wigner scaling law in the cold threshold regime and may intersect with each other. In order to interpret the mechanism and estimate the cross sections of the rotational energy transfer, we propose a minimal classical model of collision between an asymmetric double-shell ellipsoid and a point particle. The classical model reproduces the quantum scattering results and points out the attractive interactions and the potential asymmetry can affect the collision process. The resulting insights are expected to expand our interpretations of inelastic scattering and energy transfer in molecular collisions.

Stochastic model of collisional energy transfer based on the diffusion equation

Collisional energy transfer from highly excited polyatomic molecules in a heat reservoir is considered as a diffusion process in energy space. It is taken into account that the density of the vibrational states of polyatomic molecules is very high and presented by a continuous energy function. Both the average energy transfer moments per collision and these moments averaged over an ensemble of molecules have been calculated to obtain an exact analytical solution to the diffusion equation. At long times, the solution to the diffusion equation converges to the equilibrium Boltzmann distribution. The conditional probability density decays at long times with a vibrational energy relaxation time. The ensemble averages tend to equilibrium with the same characteristic time.