A single resonance Regge pole dominates the forward-angle scattering of the state-to-state F + H2 → FH + H reaction at Etrans = 62.09 meV.

The aim of the present paper is to bring clarity, through simplicity, to the important and long-standing problem: does a resonance contribute to the forward-angle scattering of the F + H2 reaction? We reduce the problem to its essentials and present a well-defined, yet rigorous and unambiguous, investigation of structure in the differential cross sections (DCSs) of the following three state-to-state reactions at a translational energy of 62.09 meV: F + H2(vi = 0, ji = 0, mi = 0) → FH(vf = 3, jf = 0, 1, 2, mf = 0) + H, where vi, ji, mi and vf, jf, mf are the initial and final vibrational, rotational and helicity quantum numbers respectively. Firstly, we carry out quantum-scattering calculations for the Fu-Xu-Zhang potential energy surface, obtaining accurate numerical scattering matrix elements for indistinguishable H2. The calculations use a time-independent method, with hyperspherical coordinates and an enhanced Numerov method. Secondly, the following theoretical techniques are employed to analyse structures in the DCSs: (a) full and Nearside-Farside (NF) partial wave series (PWS) and local angular momentum theory, including resummations of the full PWS up to second order. (b) The recently introduced "CoroGlo" test, which lets us distinguish between glory and corona scattering at forward angles for a Legendre PWS. (c) Six asymptotic (semiclassical) forward-angle glory theories and three asymptotic farside rainbow theories, valid for rainbows at sideward-scattering angles. (d) Complex angular momentum (CAM) theories of forward and backward scattering, with the Regge pole positions and residues computed by Thiele rational interpolation. Thirdly, our conclusions for the three PWS DCSs are: (a) the forward-angle peaks arise from glory scattering. (b) A broad (hidden) farside rainbow is present at sideward angles. (c) A single Regge pole contributes to the DCS across the whole angular range, being most prominent at forward angles. This proves that a resonance contributes to the DCSs for the three transitions. (d) The diffraction oscillations in the DCSs arise from NF interference, in particular, interference between the Regge pole and direct subamplitudes.

Investigation on the Mechanical Recycling of Carbon Fiber-Reinforced Polymers by Peripheral Down-Milling.

Carbon fiber-reinforced plastics (CFRPs) are composite materials that play a significant role in the growth of many industrial fields where high performance and lightness of the structures are required. At the same time, the management at the end of their life has required the development of more and more sustainable and efficient recycling solutions. Considering this, the present research work aims to investigate a mechanical recycling method and the cutting strategies able to machine CFRP components in their entirety, using a common milling machine in a job shop scheme, making a shorter supply chain, and leading to economic and environmental benefits. In detail, laminates obtained by unidirectional carbon fiber prepregs were worked through the peripheral down-milling process, by varying the spindle speed and the feed rate. The recording of the cutting forces enabled the evaluation of features such as the cutting power and the specific cutting energy. Moreover, the chips from the milling process were classified as a function of their dimensions. Finally, specimens made of chips and epoxy resin were characterized under bending conditions, to evaluate the effectiveness of using the chips from CFRP peripheral milling as the polymer's reinforcement and, in addition, to appreciate the goodness of this recycling strategy.

Benchmark Quantum Kinetics at Low Temperatures toward Absolute Zero and Role of Entrance Channel Wells on Tunneling, Virtual States, and Resonances: The F + HD Reaction.

This paper reports a study of the quantum reaction dynamics and kinetics of the F + HD reaction at low and ultralow temperatures, focusing on the range from the Wigner limit up to 50 K. Close coupling time-independent quantum reactive scattering calculations for the production of HF and DF molecules have been carried out on two potential energy surfaces differing in the description of the reaction entrance channel. This case is computationally more demanding than the cases of F with H2 and D2 ( De Fazio et al. Frontiers in Chemistry 2019 , 7 , 328 ) but offers a wider phenomenology regarding the roles of quantum mechanical effects of tunneling, of virtual states, and of resonances. The results show that at the temperatures in the cold and ultracold regimes small changes in the entrance channel long-range interaction induce surprising near threshold features. The presence of a virtual state close to the reactive threshold gives rise to a marked anti-Arrhenius behavior of the rate constants below 100 mK. This effect enhances reaction rates by about 2 orders of magnitude, making them of the same order as those at room temperature and confining the onset of the Wigner regime in the microkelvin region.

Quantum Dynamics and Kinetics of the F + H2 and F + D2 Reactions at Low and Ultra-Low Temperatures.

Integral cross sections and rate constants for the prototypical chemical reactions of the fluorine atom with molecular hydrogen and deuterium have been calculated over a wide interval of collision energy and temperature ranging from the sub-thermal (50 K) down to the ultra-cold regimes (0.5 mK). Rigorous close coupling time-independent quantum reactive scattering calculations have been carried out on two potential energy surfaces, differing only at long-range in the reactants' channel. The results show that tunnel, resonance and virtual state effects enhance under-barrier reactivity giving rise to pronounced deviations from the Arrhenius law as temperature is lowered. Within the ultra-cold domain (below 1 mK), the reactivity is governed by virtual state effects and by tunneling through the reaction barrier; in the cold regime (1 mK-1 K), the shape resonances in the entrance channel of the potential energy surface make the quantum tunneling contribution larger so enhancing cross sections and rate constants by about one order of magnitude; at higher temperatures (above 10 K), the tunneling pathway enhanced by the constructive interference between two Feshbach resonances trapped in the reaction exit channel competes with the thermally activated mechanism, as the energy gets closer to the reaction barrier height. The results show that at low temperatures cross sections and rate constants are extremely sensitive to small changes in the long-range intermolecular interaction in the entrance channel of the potential energy surface, as well as to isotopic substitution.

Non-adiabatic Quantum Dynamics of the Dissociative Charge Transfer He++H2 → He+H+H.

We present the non-adiabatic, conical-intersection quantum dynamics of the title collision where reactants and products are in the ground electronic states. Initial-state-resolved reaction probabilities, total integral cross sections, and rate constants of two H2 vibrational states, v 0 = 0 and 1, in the ground rotational state (j 0 = 0) are obtained at collision energies E coll ≤ 3 eV. We employ the lowest two excited diabatic electronic states of HeH 2 + and their electronic coupling, a coupled-channel time-dependent real wavepacket method, and a flux analysis. Both probabilities and cross sections present a few groups of resonances at low E coll, whose amplitudes decrease with the energy, due to an ion-induced dipole interaction in the entrance channel. At higher E coll, reaction probabilities and cross sections increase monotonically up to 3 eV, remaining however quite small. When H2 is in the v 0 = 1 state, the reactivity increases by ~2 orders of magnitude at the lowest energies and by ~1 order at the highest ones. Initial-state resolved rate constants at room temperature are equal to 1.74 × 10-14 and to 1.98 × 10-12 cm3s-1 at v 0 = 0 and 1, respectively. Test calculations for H2 at j 0 = 1 show that the probabilities can be enhanced by a factor of ~1/3, that is ortho-H2 seems ~4 times more reactive than para-H2.

Benchmark Quantum Mechanical Calculations of Vibrationally Resolved Cross Sections and Rate Constants on ab Initio Potential Energy Surfaces for the F + HD Reaction: Comparisons with Experiments.

Quantum scattering calculations within the time-independent approach in an extended interval of energies were performed for the title reaction on four ab initio potential energy surfaces. The calculated integral cross sections, vibrational branching ratios, and rate constants are compared with scattering experiments as well as with chemical kinetics rate data available for this system for both the HF and DF channels. The calculations on the CSZ (J. Chem. Phys. 2015, 142, 024303) and LWAL (J. Chem. Phys. 2007, 127, 174302) surfaces are in close agreement between them and reproduce satisfactorily the experimental measurements. The agreement with the experiments is improved with respect to calculations on the earlier SW (J. Chem. Phys. 1996, 104, 6515) and FXZ (J. Chem. Phys. 2008, 129, 011103) surfaces. The results presented here witness the remarkable progress made by quantum chemistry calculations in describing the interatomic interactions governing the dynamics and kinetics of this reaction. They also suggest that comparison with translationally and rotationally averaged experimental observables is not sufficient to assess the relative accuracy of highly accurate potential energy surfaces. The dynamics and kinetics calculations show that temperatures lower than 50 K or molecular beam energy spread below 1 meV must be reached to discriminate the accuracy of the LWAL and the CSZ surfaces.

Complementarity between Quantum and Classical Mechanics in Chemical Modeling. The H + HeH+ → H2 + + He Reaction: A Rigourous Test for Reaction Dynamics Methods.

In this work we present a dynamical study of the H + HeH+ → H2+ + He reaction in a collision energy range from 0.1 meV to 10 eV, suitable to be used in applicative models. The paper extends and complements a recent work [ Phys. Chem. Chem. Phys. 2014, 16, 11662] devoted to the characterization of the reactivity from the ultracold regime up to the three-body dissociation breakup. In particular, the accuracy of the quasi-classical trajectory method below the three-body dissociation threshold has been assessed by a detailed comparison with previous calculations performed with different reaction dynamics methods, whereas the reliability of the results in the high energy range has been checked by a direct comparison with the available experimental data. Integral cross sections for several HeH+ roto-vibrational states have been analyzed and used to understand the extent of quantum effects in the reaction dynamics. By using the quasi-classical trajectory method and quantum mechanical close coupling data, respectively, in the high and low collision energy ranges, we obtain highly accurate thermal rate costants until 15 000 K including all (178) the roto-vibrational bound and quasi-bound states of HeH+. The role of the collision-induced dissociation is also discussed and explicitly calculated for the ground roto-vibrational state of HeH+.

The H + HeH(+) → He + H2(+) reaction from the ultra-cold regime to the three-body breakup: exact quantum mechanical integral cross sections and rate constants.

In this work, we present a quantum mechanical scattering study of the title reaction from 1 mK to 2000 K. Total integral cross sections and thermal rate constants are compared with previous theoretical and experimental data and with simpler theoretical models to understand the range of validity of the approximations used in the previous studies. The obtained quantum reactive observables have been found to be nearly insensitive to the roto-vibrational energy of the reactants at high temperatures. More sensitive to the reactant's roto-vibrational energy are the data in the cold and ultra-cold regimes. The implications of the new data presented here in the early universe scenario are also discussed and analyzed.

Polarization of molecular angular momentum in the chemical reactions Li + HF and F + HD.

The quantum mechanical approach to vector correlation of angular momentum orientation and alignment in chemical reactions [G. Balint-Kurti and O. S. Vasyutinskii, J. Phys. Chem. A 113, 14281 (2009)] is applied to the molecular reagents and products of the Li + HF [L. Gonzalez-Sanchez, O. S. Vasyutinskii, A. Zanchet, C. Sanz-Sanz, and O. Roncero, Phys. Chem. Chem. Phys. 13, 13656 (2011)] and F + HD [D. De Fazio, J. Lucas, V. Aquilanti, and S. Cavalli, Phys. Chem. Chem. Phys. 13, 8571 (2011)] reactions for which accurate scattering information has become recently available through time-dependent and time-independent approaches. Application of the theory to two important particular cases of the reactive collisions has been considered: (i) the influence of the angular momentum polarization of reactants in the entrance channel on the spatial distribution of the products in the exit channel and (ii) angular momentum polarization of the products of the reaction between unpolarized reactants. In the former case, the role of the angular momentum alignment of the reactants is shown to be large, particularly when the angular momentum is perpendicular to the reaction scattering plane. In the latter case, the orientation and alignment of the product angular momentum was found to be significant and strongly dependent on the scattering angle. The calculation also reveals significant differences between the vector correlation properties of the two reactions under study which are due to difference in the reaction mechanisms. In the case of F + HD reaction, the branching ratio between HF and DF production points out interest in the insight gained into the detailed dynamics, when information is available either from exact quantum mechanical calculations or from especially designed experiments. Also, the geometrical arrangement for the experimental determination of the product angular momentum orientation and alignment based on a compact and convenient spherical tensor expression for the intensity of the resonance enhanced multiphoton ionization (REMPI 2 + 1) signal is suggested.

The He + H2+ → HeH+ + H reaction: ab initio studies of the potential energy surface, benchmark time-independent quantum dynamics in an extended energy range and comparison with experiments.

In this work we critically revise several aspects of previous ab initio quantum chemistry studies [P. Palmieri et al., Mol. Phys. 98, 1835 (2000); C. N. Ramachandran et al., Chem. Phys. Lett. 469, 26 (2009)] of the HeH(2)(+) system. New diatomic curves for the H(2)(+) and HeH(+) molecular ions, which provide vibrational frequencies at a near spectroscopic level of accuracy, have been generated to test the quality of the diatomic terms employed in the previous analytical fittings. The reliability of the global potential energy surfaces has also been tested performing benchmark quantum scattering calculations within the time-independent approach in an extended interval of energies. In particular, the total integral cross sections have been calculated in the total collision energy range 0.955-2.400 eV for the scattering of the He atom by the ortho- and para-hydrogen molecular ion. The energy profiles of the total integral cross sections for selected vibro-rotational states of H(2)(+) (v = 0,...,5 and j = 1,...,7) show a strong rotational enhancement for the lower vibrational states which becomes weaker as the vibrational quantum number increases. Comparison with several available experimental data is presented and discussed.

Exploring the accuracy level of new potential energy surfaces for the F + HD reactions: from exact quantum rate constants to the state-to-state reaction dynamics.

Exact quantum reactive scattering calculations in the collision energy range 1-250 meV have been carried out for both the isotopic product channels of the title system. The dynamical studies compares an ab initio potential energy surface (PES) recently appeared in the literature (J. Chem. Phys., 2008, 129, 011103) with other phenomenological PESs. Vibrational branching ratios, cross sections and rate constants are presented and compared with molecular beam scattering experiments as well as with chemical kinetics data. In particular, the agreement of the vibrational branching ratios with experimental measurements is improved with respect to previous studies on other PESs, mainly because of the presence of a broad peak in the HF(v' = 3) integral cross section completely absent in the previous simulations. This feature, observed by molecular beam experiments, is the fingerprint of a new reaction mechanism operative in the dynamics described by the new PES. A conjecture for its origin, able to explain many of its characteristic aspects, is analyzed and discussed.

Exact state-to-state quantum dynamics of the F + HD --> HF(v' = 2) + D reaction on model potential energy surfaces.

In this paper, we present the results of a theoretical investigation on the dynamics of the title reaction at collision energies below 1.2 kcal/mol using rigorous quantum reactive scattering calculations. Vibrationally resolved integral and differential cross sections, as well as product rotational distributions, have been calculated using two electronically adiabatic potential energy surfaces, developed by us on the basis of semiempirical modifications of the entrance channel. In particular, we focus our attention on the role of the exothermicity and of the exit channel region of the interaction on the experimental observables. From the comparison between the theoretical results, insight about the main mechanisms governing the reaction is extracted, especially regarding the bimodal structure of the HF(v = 2) nascent rotational state distributions. A good overall agreement with molecular beam scattering experiments has been obtained.

Exact quantum calculations of the kinetic isotope effect: cross sections and rate constants for the F+HD reaction and role of tunneling.

In this paper we present integral cross sections (in the 5-220 meV collision energy range) and rate constants (in the 100-300 K range of temperature) for the F+HD reaction leading to HF+D and DF+H. The exact quantum reactive scattering calculations were carried out using the hyperquantization algorithm on an improved potential energy surface which incorporates the effects of open shell and fine structure of the fluorine atom in the entrance channel. The results reproduce satisfactorily molecular beam scattering experiments as well as chemical kinetics data for both the HF and DF channels. In particular, the agreement of the rate coefficients and the vibrational branching ratios with experimental measurements is improved with respect to previous studies. At thermal and subthermal energies, the rates are greatly influenced by tunneling through the reaction barrier. Therefore exchange of deuterium is shown to be penalized with respect to exchange of hydrogen, and the isotopic branching exhibits a strong dependence on translational energy. Also, it is found that rotational excitation of the reactant HD molecule enhances the production of HF and decreases the reactivity at the D end, obtaining insight on the reaction stereodynamics.

Direct evaluation of the lifetime matrix by the hyperquantization algorithm: narrow resonances in the F + H2 reaction dynamics and their splitting for nonzero angular momentum.

We propose a new method for the direct and efficient evaluation of the Felix Smith's lifetime Q matrix for reactive scattering problems. Simultaneous propagation of the solution to a set of close-coupled equations together with its energy derivative allows one to avoid common problems pertinent to the finite-difference approach. The procedure is implemented on a reactive scattering code which employs the hyperquantization algorithm and the Johnson-Manolopoulos [J. Comput. Phys. 13, 455 (1973); J. Chem. Phys 85, 6425 (1986)] propagation to obtain the complete S matrix and scattering observables. As an application of the developed formalism, we focus on the total angular momentum dependence of narrow under-barrier resonances supported by van der Waals wells of the title reaction. Using our method, we fully characterize these metastable states obtaining their positions and lifetimes from Lorentzian fits to the largest eigenvalue of the lifetime matrix. Remarkable splittings of the resonances observed at J>0 are rationalized in terms of a hyperspherical model. In order to provide an insight on the decay mechanism, the Q-matrix eigenvectors are analyzed and the dominant channels populated during the decomposition of metastable states are determined. Possible relevance of the present results to reactive scattering experiments is discussed.

Lifetime of reactive scattering resonances: Q-matrix analysis and angular momentum dependence for the F+H2 reaction by the hyperquantization algorithm.

We report a study on the behavior with total angular momentum J of several resonances occurring at collision energies below or slightly above the reaction barrier in the F+H2-->HF+H reaction. Resonance positions and widths are extracted from exact time-independent quantum mechanical calculations using the hyperquantization algorithm and Smith's Q-matrix formalism which exploits complete S-matrix information. The results confirm previous work but provide much greater insight. Identification of quasi-bound states responsible for the resonances based on adiabatic models for the long-range atom-molecule interactions both in the entrance and exit channels, is successful except for the feature occurring at the lowest energy, which is found to overlap with an exit-channel resonance for J approximately 7. The two features are analyzed as overlapping resonances and their excellent Lorentzian fits, with well-behaved J-dependences of positions and widths, support the interpretation of the low-energy feature as a resonance to be associated to the triatomic transition state of the reaction. Resonance role on the reactive observables (integral cross sections and angular distributions) is investigated. The mechanism leading to forward scattering in the reactive differential cross section is commented, while the effects on rate constants, as well as the sensitivity of the resonance pattern to modification of the potential energy surface, are fully discussed elsewhere.