Product Angular Distributions Research Articles

Multistate Dynamics and Kinetics of CO2 Activation by Ta+ in the Gas Phase: Insights into Single-Atom Catalysis.

The activation of carbon dioxide (CO2) by a transition-metal cation in the gas phase is a unique model system for understanding single-atom catalysis. The mechanism of such reactions is often attributed to a "two-state reactivity" model in which the high-energy barrier of a spin state correlating with ground-state reactants is avoided by intersystem crossing (ISC) to a different spin state with a lower barrier. However, such a "spin-forbidden" mechanism, along with the corresponding dynamics, has seldom been rigorously examined theoretically, due to the lack of global potential energy surfaces (PESs). In this work, we report full-dimensional PESs of the lowest-lying quintet, triplet, and singlet states of the TaCO2+ system, machine-learned from first-principles data. These PESs and the corresponding spin-orbit couplings enable us to provide an extensive theoretical characterization of the dynamics and kinetics of the reaction between the tantalum cation (Ta+) and CO2, which have recently been investigated experimentally at high collision energies using crossed beams and velocity map imaging, as well as at thermal energies using a selected-ion flow tube apparatus. The multistate quasi-classical trajectory simulations with surface hopping reproduce most of the measured product translational and angular distributions, shedding valuable light on the nonadiabatic reaction dynamics. The calculated rate coefficients from 200 to 600 K are also in good agreement with the latest experimental measurements. More importantly, these calculations revealed that the reaction is controlled by intersystem crossing, rather than potential barriers.

Photodissociation dynamics of the ethyl radical via the Ã2A'(3s) state: H-atom product channels and ethylene product vibrational state distribution.

The photodissociation dynamics of jet-cooled ethyl radical (C2H5) via the Ã2A'(3s) states are studied in the wavelength region of 230-260nm using the high-n Rydberg H-atom time-of-flight (TOF) technique. The H + C2H4 product channels are reexamined using the H-atom TOF spectra and photofragment translational spectroscopy. A prompt H + C2H4(X̃1Ag) product channel is characterized by a repulsive translational energy release, anisotropic product angular distribution, and partially resolved vibrational state distribution of the C2H4(X̃1Ag) product. This fast dissociation is initiated from the 3s Rydberg state and proceeds via a H-bridged configuration directly to the H + C2H4(X̃1Ag) products. A statistical-like H + C2H4(X̃1Ag) product channel via unimolecular dissociation of the hot electronic ground-state ethyl (X̃2A') after internal conversion from the 3s Rydberg state is also examined, showing a modest translational energy release and isotropic angular distribution. An adiabatic H + excited triplet C2H4(ã3B1u) product channel (a minor channel) is identified by energy-dependent product angular distribution, showing a small translational energy release, anisotropic angular distribution, and significant internal excitation in the C2H4(ã3B1u) product. The dissociation times of the different product channels are evaluated using energy-dependent product angular distribution and pump-probe delay measurements. The prompt H + C2H4(X̃1Ag) product channel has a dissociation time scale of <10ps, and the upper bound of the dissociation time scale of the statistical-like H + C2H4(X̃1Ag) product channel is <5ns.

Polarized fusion and potential in situ tests of fuel polarization survival in a tokamak plasma

The use of spin-polarized fusion fuels would provide a significant boost towards the ignition of a burning plasma. The cross section for D + T → α + n, would be increased by 1.5 if the fuels were injected with parallel polarization. Furthermore, our simulations demonstrate additional non-linear power gains in large-scale machines such as ITER, due to increased alpha heating. Such benefits require the survival of spin polarizations for periods comparable to the particle confinement time. During the 1980s, calculations predicted that polarizations could survive a plasma environment, although concerns persisted regarding the cumulative impacts of wall recycling. In that era, technical challenges prevented direct tests and left the large scale fueling of a power reactor beyond reach. Over the last decades, this situation has changed dramatically. Detailed simulations of ITER have predicted negligible wall recycling in a high-power reactor, and recent advances in laser-driven sources project the capability of producing large quantities of ∼100% polarized D and T. The remaining crucial step is an in-situ demonstration of polarization survival in a plasma. For this, we outline a measurement strategy using the isospin-mirror reaction, D + 3He → α + p. Polarized 3He avoids the complexities of handling tritium, while encompassing the same spin-physics. We evaluate two methods of delivering deuterium, using dynamically polarized Lithium-Deuteride (with vector polarization PV D of 70%) or frozen-spin Hydrogen-Deuteride (with PV D of 40%), together with a method of injecting optically-pumped 3He (with 65% polarization). Pellets of these materials all have long polarization decay times (∼6 min for LiD at 2 K, ∼2 months for HD at 2 K, and ∼3 d for 3He at 77 K), all far greater than a plasma shot in a research tokamak such as DIII-D (∼20 s). Both species can be propelled from a single cryogenic injection gun. We review plasma requirements and strategies for detecting polarization survival. Polarization alters both fusion yields and the angular distribution of fusion products, and each of these provides a potential signal. In this paper we simulate a selection of shots with similar characteristics in a future high-Tion H plasma, and find ratios of yields from shots with fuel spins parallel and antiparallel reaching 1.3 (HD + 3He) to 1.6 (LiD + 3He) over a wide range of poloidal angles. (A companion paper finds sensitivity to fusion product angular distributions as reflected in the pitch angles of protons and alphas reaching the plasma facing wall.)

Investigating the Rydberg states and photodissociation dynamics of Kr2using velocity map imaging

Although the krypton dimer, Kr2, is a prototypical weakly bound van der Waals complex in its ground electronic state, the excited states of Kr2exhibit many and various interactions. Resonance-enhanced multiphoton ionization and velocity map imaging provide an avenue to explore the electronic structure and photofragmentation dynamics of Kr2in the vacuum ultraviolet region. By monitoring photofragmentation product channels and recoil anisotropy distributions, one can gain insights into excited state symmetries and lifetimes, which can aid in interpreting spectroscopy. Here, we study the spectroscopy and photodissociation dynamics of Kr2in the 91 000–94 500 cm−1region. We record and assign photofragment product channels for 32 vibronic bands corresponding to seven electronic transitions. We also identify two previously unobserved vibronic band systems, which we assign as the Kr2 5p [5/2]3 [Formula: see text] and 5p [3/2]2[Formula: see text] transitions. Velocity map images show photofragments arising from predissociation of the neutral Rydberg states and from dissociative photoionization at the n &gt; 2 photon level. We also observe variation in branching ratios between the predissociative and dissociative photoionization channels depending on the lifetime of the intermediate; longer lived states favour higher dissociative photoionization yields and exhibit β6anisotropy parameters for predissociation product channels, indicating “rotational smearing” of the product angular distributions.

Deciphering Dynamics of the Cl + SiH4 → H + SiH3Cl Reaction on a Machine Learning Made Globally Accurate Full-Dimensional Potential Energy Surface

Chemical reaction dynamics needs the joint effort from both experiment and theory, and theory is useful to rationalize the experimental results by offering intimate details of chemical reaction dynamics and to explore new reaction pathways. With the aid of machine learning, we develop here an accurate full-dimensional potential energy surface (PES) for the reaction between Cl + SiH4. This PES can describe well the hydrogen abstraction channel to HCl + SiH3. It can also give a good description for the hydrogen substitution channel to H + SiH3Cl, which is the focus of the current study and has never been reported by theory. The dynamics of this substitution channel is revealed in detail by calculating ample quasi-classical trajectories (QCTs) on the new PES. The computed product angular distributions are in good agreement with the only crossed molecular beam experiment. Both theory and experiment suggest that this channel takes place mainly via the typical SN2 inversion mechanism. Theory reveals that there also exists a novel torsion mechanism for the substitution channel. Two dynamic mechanisms are analyzed in detail. The present detailed theoretical dynamics study sheds insightful and novel understanding for this fundamentally important chemical reaction.

The N(2D) + CH2CHCN (Vinyl Cyanide) Reaction: A Combined Crossed Molecular Beam and Theoretical Study and Implications for the Atmosphere of Titan.

The reaction of electronically excited nitrogen atoms, N(2D), with vinyl cyanide, CH2CHCN, has been investigated under single-collision conditions by the crossed molecular beam (CMB) scattering method with mass spectrometric detection and time-of-flight (TOF) analysis at the collision energy, Ec, of 31.4 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) have been performed to assist in the interpretation of the experimental results and characterize the overall reaction micromechanism. Statistical (Rice–Ramsperger–Kassel–Marcus, RRKM) calculations of product branching fractions (BFs) on the theoretical PES have been carried out at different values of temperature, including the one corresponding to the temperature (175 K) of Titan’s stratosphere and at a total energy corresponding to the Ec of the CMB experiment. According to our theoretical calculations, the reaction is found to proceed via barrierless addition of N(2D) to the carbon–carbon double bond of CH2=CH–CN, followed by the formation of cyclic and linear intermediates that can undergo H, CN, and HCN elimination. In competition, the N(2D) addition to the CN group is also possible via a submerged barrier, leading ultimately to N2 + C3H3 formation, the most exothermic of all possible channels. Product angular and TOF distributions have been recorded for the H-displacement channels leading to the formation of a variety of possible C3H2N2 isomeric products. Experimentally, no evidence of CN, HCN, and N2 forming channels was observed. These findings were corroborated by the theory, which predicts a variety of competing product channels, following N(2D) addition to the double bond, with the main ones, at Ec = 31.4 kJ/mol, being six isomeric H forming channels: c-CH(N)CHCN + H (BF = 35.0%), c-CHNCHCN + H (BF = 28.1%), CH2NCCN + H (BF = 26.3%), c-CH2(N)CCN(cyano-azirine) + H (BF = 7.4%), trans-HNCCHCN + H (BF = 1.6%), and cis-HNCCHCN + H (BF = 1.3%), while C–C bond breaking channels leading to c-CH2(N)CH(2H-azirine) + CN and c-CH2(N)C + HCN are predicted to be negligible (0.02% and 0.2%, respectively). The highly exothermic N2 + CH2CCH (propargyl) channel is also predicted to be negligible because of the very high isomerization barrier from the initial addition intermediate to the precursor intermediate able to lead to products. The predicted product BFs are found to have, in general, a very weak energy dependence. The above cyclic and linear products containing an additional C–N bond could be potential precursors of more complex, N-rich organic molecules that contribute to the formation of the aerosols on Titan’s upper atmosphere. Overall, the results are expected to have a significant impact on the gas-phase chemistry of Titan’s atmosphere and should be properly included in the photochemical models.

Observation of Competitive Nonadiabatic Photodissociation Dynamics of H2S+ Cations.

A comprehensive understanding of dissociation mechanisms is of fundamental importance in the photochemistry of small molecules. Here, we investigated the detailed photodissociation dynamics of H2S+ near 337 nm by using the velocity map ion imaging technique together with the theoretical characterizations by developing global full-dimensional potential energy surfaces (PESs). Rotational state resolved images were acquired for the S+(4S) + H2 product channel. Significant changes in product total kinetic energy release distributions and angular distributions have been observed within a small excitation photon energy range of 5 wavenumbers. Analysis based on the full-dimensional PESs reveals that two nonadiabatic pathways determined by the transition state connecting two minima on the 12A' state are responsible for the dramatic variation of observed product distributions. The current study has directly witnessed the competitive photodissociation mechanisms controlled by a critical energy point on the PES, thereby providing in-depth insight into the nonadiabatic dynamics in photochemistry.

Elastic scattering and boron, lithium, and α -particle production in the Be9 + V51 reaction

Background: Experimental and theoretical investigation of breakup coupling effects due to different cluster structures ($^{8}\mathrm{Be}+n$ and $^{5}\mathrm{He}+\ensuremath{\alpha}$), relative importance of neutron or $^{5}\mathrm{He}/\ensuremath{\alpha}$ transfer, and their contribution to $\ensuremath{\alpha}$ production are important to understand reaction mechanism in a weakly bound projectile ($^{9}\mathrm{Be}$) near the Coulomb barrier.Purpose: Breakup coupling effect on elastic scattering and measurement of angular distributions and energy spectra of $\ensuremath{\alpha}$ particles produced through breakup, transfer, and complete fusion processes to disentangle their relative contributions and to investigate the relative importance of breakup followed by fusion (breakup-fusion) are compared to transfer.Methods: Elastic scattering, inclusive $\ensuremath{\alpha}$ production, lithium, and boron production cross sections have been measured for the $^{9}\mathrm{Be}+^{51}\mathrm{V}$ system above Coulomb barrier energies. Continuum-discretized-coupled-channels (CDCC) breakup coupling effect using $^{8}\mathrm{Be}+n$ and $^{5}\mathrm{He}+\ensuremath{\alpha}$ cluster configurations have been investigated. Coupled reaction channels (CRC) calculations for $1\mathit{p}, 1\mathit{d}$, and $1\mathit{n}$ stripping and $1\mathit{p}, 1\mathit{d}$ pickup leading to $^{8}\mathrm{Li}+^{52}\mathrm{Cr}, ^{7}\mathrm{Li}+^{53}\mathrm{Cr}, ^{8}\mathrm{Be}+^{52}\mathrm{V}$, and $^{10}\mathrm{B}+^{50}\mathrm{Ti}, ^{11}\mathrm{B}+^{49}\mathrm{Ti}$, respectively, were performed and compared with the experimental data. Theoretical calculations for the estimation of various reaction channels contributing to $\ensuremath{\alpha}$ production have been performed with CDCC and CRC methods using the fresco code.Results: Global optical model parameters for the $^{9}\mathrm{Be}$ projectile describe the elastic scattering data very well and the optical model fit improves the ${\ensuremath{\chi}}^{2}$ slightly. CRC calculations show a major contribution in the production of lithium through $1\mathit{p}, 1\mathit{d}$ stripping and boron through $1\mathit{p}, 1\mathit{d}$ pickup reactions. $\ensuremath{\alpha}$ production angular and energy distributions are obtained, and direct $\ensuremath{\alpha}$ production is described with contributions from noncapture breakup, breakup-fusion, and transfer reactions.Conclusions: Breakup coupling for $^{5}\mathrm{He}+\ensuremath{\alpha}$ and $^{8}\mathrm{Be}+n$ cluster structures shows a repulsive and attractive coupling effect on elastic scattering, respectively. The $^{8}\mathrm{Be}+n$ cluster structure also shows a dipole polarization effect by suppressing the Coulomb rainbow compared to the $^{5}\mathrm{He}+\ensuremath{\alpha}$ cluster structure. Kinematic analysis of the $\ensuremath{\alpha}$ particles energy spectra suggest that $\ensuremath{\alpha}$ production is dominated by breakup-fusion over cluster transfer. CRC calculations suggest that $1\mathit{p}, 1\mathit{d}$ stripping and pickup reactions are a major contributor to lithium and boron production cross sections.

Crossed Molecular Beam Study of the H + HD → H2 + D Reaction at 0.60 and 1.26 eV Using the Near-Threshold Ionization Velocity Map Ion Imaging

By using the 1 + 1' near-threshold ionization velocity map ion imaging technique, state-to-state reactive differential cross sections have been measured for the H + HD → H2 + D reaction. High-resolution images of the D products, with the rotational states of the H2 co-products clearly resolved, were acquired at the collision energies of 0.60 and 1.26 eV, respectively. It is found that the angular distribution is predominantly backward-scattering at the collision energy of 0.60 eV. However, at 1.26 eV, where the collision energy is higher, the angular distribution becomes forward-backward-scattering. Notably, at both collision energies, the main peaks of backward-scattered products gradually shift from backward toward sideways direction as the rotational quantum number of H2 increases. Moreover, in the forward direction, fast angular oscillations, which are induced by specific partial waves have also been observed at 1.26 eV. These features show a strong correlation between the product states and angular distributions and also indicate the unique role of partial waves in quantum reactive scattering.

Role of Low Energy Resonances in the Stereodynamics of Cold He + D2 Collisions.

In recent experiments using the Stark-induced adiabatic Raman passage technique, Zhou et al. ( J. Chem. Phys. 2021, 154, 104309; Science 2021, 374, 960-964) measured the product's angular distribution for the collisions between He and aligned D2 molecules at cold collision energies. The signatures of the angular distributions were attributed to an [Formula: see text] = 2 resonance that governs scattering at low energies. A first-principles quantum mechanical treatment of this problem is presented here using a highly accurate interaction potential for the He-H2 system. Our results predict a very intense [Formula: see text] = 1 resonance at low energies, leading to angular distributions that differ from those measured in the experiment. A good agreement with the experiment is achieved only when the [Formula: see text] = 1 resonance is artificially removed, for example, by excluding the lowest energies present in the experimental velocity distribution. Our analysis revealed that neither the position nor the intensity of the [Formula: see text] = 1 resonance significantly changes when the interaction potential is modified within its predicted uncertainties. Energy-resolved measurements may help to resolve the discrepancy.

Feshbach resonances in D + HD(v=1, j=0) reaction at low collision energies.

Feshbach resonances in D + HD(v=1, j=0) reaction are studied by using the time-independent quantum method. The integral cross section (ICS) results present three Feshbach resonance peaks, which are different from H + HD(v=1, j=0) reaction dominated by only one peak. These resonances are attributed to coupling with adiabatic effective potentials of D + HD(v=1, j=1) reaction, and the most obvious peak is contributed by J= 1 at 83.16 cm-1 collision energy. For J=0 and 2, the resonances are related with the same L partial wave and present a double-peak structure in total ICS. The characteristics of product angular distribution show that the resonance of J=1 is long-lived, while the lifetimes are relatively shorter for the resonance of J= 0 and 2.

Photodissociation Dynamics of Vinoxy Radical via the B̃2A″ State: The H + CH2CO Product Channel.

Photodissociation dynamics of the jet-cooled vinoxy radical (CH2CHO) via the B̃2A″ state was studied in the near-ultraviolet (near-UV) region of 308-328 nm using high-n Rydberg H atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The vinoxy radical beam was produced by 193 nm photolysis of ethyl vinyl ether followed by supersonic expansion. The H + CH2CO product channel was observed directly in the H atom TOF spectra. The H atom photofragment yield (PFY) spectra were obtained by integrating the H atom TOF spectra and measuring the H atom REMPI signals, and showed several vibronic bands of the B̃2A″ state. The translational energy distributions of the H + CH2CO products, P(ET)'s, were obtained at several vibronic transitions. The P(ET) distributions were broad, peaking at a low energy of ∼3500 cm-1. The product translational energy release was moderate; the average translational energy release in the maximum available energy, ⟨fT⟩, was in the range of 0.24-0.27. The product angular distributions in this wavelength region were slightly anisotropic, with the β parameter in the range of 0.10-0.24. The near-UV photodissociation mechanism of the H + CH2CO product channel of the vinoxy radical is consistent with unimolecular dissociation on the electronic ground state (X̃2A″) following internal conversion from the B̃2A″ state to the Ã2A' state and then to the X̃2A″ state (although unimolecular dissociation from the first excited Ã2A' may also contribute).

Non-adiabatic quantum dynamics studies of the Mg+(3p) + D2 → MgD+ + D reaction

Non-adiabatic quantum dynamics study of the Mg + (3p) + D 2 reaction was carried out by using the time-dependent wave packet method. The results show that there is the triatomic complex supported by the well along the reaction path, which is manifested as metastable resonances on the probability curves. The MgD + products are obtained via a non-adiabatic pathway, and the reaction is more efficient than the quenching progress at the selected collision energies. The product angular distributions present obvious forward scattering bias, and the weak backward scatterings are mainly contributed by the new partial waves that are opened as the collision energy increases. Further rovibrational state-resolved results reflect that the predominant forward scattering correlates with the internally hot products and the backward-scattered products occupy the colder vibrational and rotational states.

Ultraviolet Photodissociation Dynamics of the Cyclohexyl Radical: The H-Atom Product Channel.

The ultraviolet (UV) photodissociation dynamics of the jet-cooled cyclohexyl (c-C6H11) radical is studied using the high-n Rydberg atom time-of-flight (HRTOF) technique. The cyclohexyl radical is produced by the 193 nm photodissociation of chlorocyclohexane and bromocyclohexane and is examined in the photolysis wavelength region of 232-262 nm. The H-atom photofragment yield (PFY) spectrum contains a broad peak centered at 250 nm, which is in good agreement with the UV absorption spectrum of the cyclohexyl radical and assigned to the 3p Rydberg states. The translational energy distributions of the H-atom loss product channel, P(ET)'s, are bimodal, with a slow (low ET) component peaking at ∼6 to 7 kcal/mol and a fast (high ET) component peaking at ∼44-48 kcal/mol. The fraction of the average translational energy in the total excess energy, ⟨fT⟩, is in the range of 0.16-0.25 in the photolysis wavelength region of 232-262 nm. The H-atom product angular distribution of the slow component is isotropic, while that of the fast component is anisotropic with an anisotropy parameter of β ≈ 0.5-0.7. The bimodal product translational energy and angular distributions indicate two dissociation pathways to the H + C6H10 products in cyclohexyl. The high-ET anisotropic component is from a repulsive, prompt dissociation on a repulsive potential energy surface coupling with the Rydberg excited states to produce H + cyclohexene. The low-ET isotropic component is consistent with the unimolecular dissociation of hot radical on the ground electronic state after internal conversion from the Rydberg states. The similarity of the photodissociation dynamics of the cyclohexyl radical to the previously studied small linear and branched alkyls expands on the understanding of the dissociation dynamics of alkyl radicals to include larger cyclic alkyl radicals.

A Full-Dimensional Potential Energy Surface and Dynamics of the Multichannel Reaction between H and HO2.

In addition to its vital significance in combustion and atmospheric chemistry, the reaction between H' and HO2 on the ground triplet state represents a prototype with multiple product channels, including H2 + O2, OH + OH, O + H2O, and H + H'O2. In this work, a full-dimensional accurate potential energy surface (PES) for the title reaction was developed to provide reliable descriptions for all dynamically relevant regions. Using this PES, we adopted the quasi-classical trajectory approach to study the corresponding reaction dynamics, including the reactivity of each product channel and the associated product branching ratio, the product energy distributions, product angular distributions, and associated microscopic mechanisms. For representing distributions of the product energies, such as product translational energy as well as product rotational and vibrational energies, both the traditional histogram and the kernel density estimation (KDE) methods were used and compared. It seems that the features of the resulting distributions in this work are very similar to each other among different methods. The KDE method is suggested for statistics, particularly for those populations with small oscillations in the histogram plot.

Theoretical study of the Cl(2P) + SiH4 reaction: global potential energy surface and product pair-correlated distributions. Comparison with experiment.

For the theoretical study of the title reaction, an analytical full-dimensional potential energy surface named PES-2021 was developed for the first time, by fitting high-level explicitly-correlated ab initio data. This reaction presented high exothermicity, (298 K) = -11.6 kcal mol-1, reproducing the experimental evidence; it is a barrierless reaction and no intermediate complexes were found. PES-2021 is a continuous and smooth potential energy surface, it includes intuitive concepts in its development and fitting, such as stretching and bending nuclear motions, and it presents analytical first energy derivatives. Based on PES-2021, kinetics and dynamics studies were carried out using quasi-classical trajectory calculations. In the kinetics study, over the temperature range 300-450 K, we observed that rate constants were practically independent of temperature, with an almost zero activation energy, as compared to 0.0 and -0.48 kcal mol-1 experimentally reported. In this kinetics study the role of the spin-orbit effect on reactivity was analysed. In the dynamics study, different product pair-correlated dynamics properties were compared with the only experimental evidence: product energy partition, product vibrational distribution, product angular distribution and product speed distribution. We observed two mechanisms of reaction, a stripping mechanism associated with large impact parameters and forward scattering, and an indirect mechanism associated with sideways-backward scattering related with "nearly-trapped" trajectories due to the product rotation. In general, theoretical results reasonably simulate the experimental measurements when they consider some rotational and vibrational constraints as well as binning techniques to mimic a quantum-mechanical behaviour. Although the agreement is not quantitative, the present results shed light on the mechanism of this difficult polyatomic reactive system.

Quasi-classical trajectory investigation of H + SO2 → OH + SO reaction on full-dimensional accurate potential energy surface

The reaction H+SO2→OH+SO is important in the combustion and atmospheric chemistry, as well as the interstellar medium. It also represents a typical complex-forming reaction with deep complexes, serving as an ideal candidate for testing various kinetics theories and providing interesting reaction dynamical phenomena. In this work, we reported a quasi-classical trajectory study of this reaction on our previously developed accurate full-dimensional potential energy surface. The experimental thermal rate coefficients over the temperature range 1400 K≤T≤2200 K were well reproduced. For the reactant SO2 being sampled at the ground ro-vibrational state, the calculated integral cross sections increased slightly along the collision energy ranging from 31.0 kcal/mol to 40.0 kcal/mol, and then became essentially flat at the collision energy within 40.0−55.0 kcal/mol. The product angular distributions are almost symmetric with nearly identical backward-forward double peak structure. The products OH and SO vibrational state distributions were also analyzed.

The MONDO Tracker: Characterisation and Study of Secondary Ultrafast Neutrons Production in Carbon Ion Radiotherapy

Secondary neutrons produced in Particle Therapy (PT) treatments are responsible for the delivery of a large fraction of the out-of-target dose as they feebly interact with the patient body. To properly account for their contribution to the total dose delivered to the patient, a high precision experimental characterisation of their production energy and angular distributions is eagerly needed. The experimental challenge posed by the detection and tracking of such neutrons will be addressed by the MONDO tracker: a compact scintillating fibres detector exploiting single and double elastic scattering interactions allowing for a complete neutron four momentum reconstruction. To achieve a high detection efficiency while matching the fibres (squared, 250 $\mu$m side) high granularity, a single photon sensitive readout has been developed using the CMOS based SPAD technology. The readout sensor, with pixels of $125\times250 \micro\meter^2$ size, will be organised in tiles covering the full detector surface and will implement an auto-trigger strategy to identify the events of interest. The expected detector performance in the context of neutron component characterisation in PT treatments delivered using carbon ions has been evaluated using a Monte Carlo simulation accounting for the detector response and the neutrons production spectra.

State-to-state predissociation dynamics of hydroxyl radical via the A2Σ+ state

ABSTRACT Photo-predissociation dynamics of jet-cooled hydroxyl radical (OH) via several rovibrational levels (v′ = 2–4, N′ = 0–2, J′ = 0.5–2.5, F 1) in the A2Σ+ state are studied using the high–n Rydberg-atom time-of-flight (HRTOF) technique. Spin–orbit branching fractions and angular distributions of the H(2S) + O(3PJ = 2,1,0) product channels are measured in the product translational energy distributions. The A2Σ+ v′ = 2 and 3 states of OH predissociate predominantly via the single 14Σ− repulsive state, while the A2Σ+ v′ = 4 state predissociates via the 14Σ−, 12Σ−, and 14Π repulsive states and quantum interferences among these dissociation pathways play an important role in the O(3PJ = 2,1,0) product fine-structure state distribution. The experimental O(3PJ) product spin–orbit branching ratios are in excellent agreement with the full quantum multichannel scattering calculations that include all the interactions in the crossing region, recoupling zone, and asymptotic zone [Parlant and Yarkony, J. Chem. Phys. 110, 363 (1999)]. The product angular distributions strongly depend on the rotational transitions and rotational levels in the A2Σ+ state. The measured anisotropy parameters are in reasonable agreement with predictions from the simulation programme (Betaofnu) [Kim et al., J. Chem. Phys. 125, 133316 (2006)], using dissociation lifetime, excitation frequency, rotational level, and rotational constant. The predissociation time scales of OH A2Σ+ are determined to be 130 ± 30 ns and ≥ 14 ± 3 ps for the v′ = 2, N′ = 2, J′ = 2.5 and v′ = 4, N′ = 0, J′ = 0.5 levels, respectively.

VUV photodissociation of DNCO: dynamics of the D atom elimination channel

The D atom Rydberg tagging time-of-flight technique was applied to investigate the photodissociation dynamics of DNCO in the vacuum ultraviolet 133–137 nm region. The D atom product was detected and the corresponding product translational energy distributions and angular distributions were obtained. Three product channels, D + NCO(X2Π), D + NCO(A2Σ+) and D + NCO(B2Π), which arise from different dissociation pathways have been observed. It is found that the D + NCO(X2Π) channel involves two different dissociation pathways; one is via internal conversion from the excited state to the S0 state, and the other is via internal conversion from the excited state to the S1 state. The D + NCO(A2Σ+) channel was ascribed to be from dissociation on S2 surface, and the D + NCO(B2Π) channel possibly come from a relatively slow dissociation process. Vibrational structures observed in the D + NCO(A2Σ+) channel shows that there is dominant bending with a little stretching vibrational excitation of NCO(A2Σ+). This is consistent with what has been found in the previous study following VUV photodissociation of HNCO in a similar wavelength region.