Roaming Reaction Research Articles

UV-Induced Reaction Pathways in Bromoform Probed with Ultrafast Electron Diffraction.

For many chemical reactions, it remains notoriously difficult to predict and experimentally determine the rates and branching ratios between different reaction channels. This is particularly the case for reactions involving short-lived intermediates, whose observation requires ultrafast methods. The UV photochemistry of bromoform (CHBr3) is among the most intensely studied photoreactions. Yet, a detailed understanding of the chemical pathways leading to the production of atomic Br and molecular Br2 fragments has proven challenging. In particular, the role of isomerization and/or roaming and their competition with direct C-Br bond scission has been a matter of continued debate. Here, gas-phase ultrafast megaelectronvolt electron diffraction (MeV-UED) is used to directly study structural dynamics in bromoform after single 267 nm photon excitation with femtosecond temporal resolution. The results show unambiguously that isomerization contributes significantly to the early stages of the UV photochemistry of bromoform. In addition to direct C-Br bond breaking within <200 fs, formation of iso-CHBr3 (Br-CH-Br-Br) is observed on the same time scale and with an isomer lifetime of >1.1 ps. The branching ratio between direct dissociation and isomerization is determined to be 0.4 ± 0.2:0.6 ± 0.2, i.e., approximately 60% of molecules undergo isomerization within the first few hundred femtoseconds after UV excitation. The structure and time of formation of iso-CHBr3 compare favorably with the results of an ab initio molecular dynamics simulation. The lifetime and interatomic distances of the isomer are consistent with the involvement of a roaming reaction mechanism.

Direct tracking of H2 roaming reaction in real time

Roaming is an unconventional type of molecular reaction where fragments, instead of immediately dissociating, remain weakly bound due to long-range Coulombic interactions. Due to its prevalence and ability to form new molecular compounds, roaming is fundamental to photochemical reactions in small molecules. However, the neutral character of the roaming fragment and its indeterminate trajectory make it difficult to identify experimentally. Here, we introduce an approach to image roaming, utilizing intense, femtosecond IR radiation combined with Coulomb explosion imaging to directly reconstruct the momentum vector of the neutral roaming H2, a precursor to H3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{{{{{\\rm{H}}}}}}}}_{3}}^{+}$$\\end{document} formation, in acetonitrile, CH3CN. This technique provides a kinematically complete picture of the underlying molecular dynamics and yields an unambiguous experimental signature of roaming. We corroborate these findings with quantum chemistry calculations, resolving this unique dissociative process.

The Influence of Hydrogen Bonds on the Roaming Reaction.

Roaming bypasses the conventional transition state and is a significant reaction pathway due to the unusual energy distributions of its products; however, its reaction pathway under external environmental interactions remains unclear. Herein, we report for the first time the roaming process of nitrobenzene, which is influenced by the hydrogen bonds (H-bonds) between nitro- and phenyl radicals and water molecules in the gas phase. Notably, despite the fact that the single water structure produces a higher but narrower barrier, whereas the double water structure leads to a lower but wider barrier, the roaming reaction still occurs. The underlying mechanism responsible for these influences of H-bonds is ascribed to the dramatically changed polarization and correlation interactions between the roaming radicals. The reaction rates and thermal perturbation probabilities are also remarkably influenced due to the presence of the H-bonds, by approximately 2 orders of magnitude. It is anticipated that this work will encourage the promising feasibility of introducing environmental molecules to modulate the roaming reaction.

The 2-pyridone/2-hydroxypyridine tautomerism in gas phase: An excited state roaming reaction.

Multiconfigurational methods (CASSCF and CASPT2) were employed to gain a new understanding of the mechanism of the gas-phase phototautomerization of 2-pyridone/2-hydroxypyridine. Potential energy curves and crossing points of the low-lying excited states were analyzed. The results show that the tautomerization only occurs from 2-pyridone to 2-hydroxypyridine after electronic excitation to the S1 (ππ*) state. From this state, the system would be able to reach a conical intersection between S1 and the dissociative S2 (πσ*) due to vibrational effects. Then, it can evolve to the hydroxy form in its ground state by reaching an intersection seam between the S0 and the πσ* states. For this to happen, a roaming process responsible for the hydrogen atom migration would be required; otherwise, the system would revert to the 2-pyridone tautomer. The unfeasibility of the reverse process after optical excitation from the lactim to the lactam form is explained by the great amount of energy needed to reach the conical intersection between the ππ* and πσ* states. These findings would provide new insights into the understanding of the photophysics and photochemistry of a primordial heterocycle, considered a prebiotic model known to be found in interstellar clouds.

High-Temperature Dissociation of Neopentanol: Shock Tube/Photoionization Mass Spectrometry Studies

The pyrolysis mechanism of 2,2-dimethylpropan-1-ol (neopentanol) has been investigated at high temperatures (1128-1401K) and high pressures (5 and 15 bar). The experiments were performed in a miniature shock tube coupled to a time-of-flight mass spectrometer. Cations were generated by tunable vacuum ultraviolet photoionization resulting in multidimensional data sets containing mass and photoionization spectra and the time histories of species. At the elevated temperatures and pressures of this work, neopentanol was determined to dissociate primarily by the scission of a C-C bond yielding tert-butyl and hydroxymethyl radicals. These promptly form isobutene and formaldehyde by H-atom elimination. In the structurally similar molecule neopentane, roaming radical reactions have previously been found to be important under conditions close to the present work (1260-1459 K, 1.1 bar). There are two possible roaming radical reactions for neopentanol. However, no experimental evidence for these reactions was found at the elevated pressures in this study, and the dissociation of neopentanol is dominated by bond scission yielding radical products.

Orbiting resonances in formaldehyde reveal coupling of roaming, radical, and molecular channels.

The roaming chemical reaction mechanism involves near-dissociation of an energized molecule to radicals that leads instead to intramolecular reaction after reorientation at long range. Surprisingly, no clear quantum signatures of roaming have been observed to date, despite the quantum nature of the roaming event. We found evidence of quantum dynamics in the photodissociation of formaldehyde near the roaming threshold. This is ascribed to resonances associated to H+HCO(Ka = 1) that have a profound impact on the CO rotational and translational energy distributions and cause the roaming fraction to vary by a factor of 2 over an energy range of 10 cm–1. The roaming pathway serves both to modulate and report on the complex vibrational dynamics and coupling among the three dissociation pathways in the excited molecule as it decays to products.

Filming ultrafast roaming-mediated isomerization of bismuth triiodide in solution

Roaming reaction, defined as a reaction yielding products via reorientational motion in the long-range region (3 – 8 Å) of the potential, is a relatively recently proposed reaction pathway and is now regarded as a universal mechanism that can explain the unimolecular dissociation and isomerization of various molecules. The structural movements of the partially dissociated fragments originating from the frustrated bond fission at the onset of roaming, however, have been explored mostly via theoretical simulations and rarely observed experimentally. Here, we report an investigation of the structural dynamics during a roaming-mediated isomerization reaction of bismuth triiodide (BiI3) in acetonitrile solution using femtosecond time-resolved x-ray liquidography. Structural analysis of the data visualizes the atomic movements during the roaming-mediated isomerization process including the opening of the Bi-Ib-Ic angle and the closing of Ia-Bi-Ib-Ic dihedral angle, each by ~40°, as well as the shortening of the Ib···Ic distance, following the frustrated bond fission.

Duality of roaming mechanism in H2CO

Chemical Physics The phenomenon of roaming in chemical reactions (that is, bypassing the minimum energy pathway from unlikely geometries) has attracted a great deal of attention in the chemical reaction dynamics community over the past decade and still demonstrates unexpected results. Using velocity-map imaging of state-selected H2 products of H2CO photodissociation, Quinn et al. discovered the bimodal structure of rotational distribution of the other product fragment, CO. Quasiclassical trajectories showed that this bimodality originates from two distinctive reaction pathways that proceed by the trans or cis configuration of O–C–H⋯H, leading to high or low rotational excitations of CO, respectively. Whether such a mechanism is present in the many other chemical reactions for which roaming reaction pathways have been reported is yet to be determined. Science , this issue p. [1592][1] [1]: /lookup/doi/10.1126/science.abc4088

Direct Production of CH(A2Δ) Radical from Intense Femtosecond Near-IR Laser Pulses.

CH(A2Δ) radical formation was observed in bromoform and methanol vapor in argon plasma with near-infrared femtosecond laser pulses (43 fs, 1030 nm, 100 kHz, 250 μJ/pulse). The beam was focused with an achromatic lens, creating very high intensity in the plasma that caused Coulomb explosion (calculated intensity was ∼1.1 × 1016 W/cm2 in the focal point). The emitted fluorescence light was measured with high spectral (1-10 cm-1) and temporal resolution (5 ns) with an FT-Vis spectrometer. The step-scan technique allowed the reconstruction of the time-resolved fluorescence spectra from CH(A-X) emission. The emission from atomic lines such as H, Br, C, and O was observed and also from C+ cations and CH and C2 radicals. This indicates that in a significant portion of these organic molecules, all chemical bonds were cleaved in the Coulomb explosion. For both organics, the peak maximum of the CH(A) emission occurred at about 10 ns after excitation by the femtosecond pulse. After the maximum, a rapid emission decay was observed in the case of bromoform (monoexponential decay, t = 10 ns). The fluorescence decay was biexponential when methanol was used as the source for CH(A) generation. It can be assumed that CH(A) generation involved a fast and a slower path with some secondary reactions via the stepwise loss of hydrogen atoms from the CH3 group. The time constants were t1 = 7.8-8.3 ns and t2 = 78-82 ns for the fast and slow components, respectively, and very similar values were obtained at 10 and 25 mbar total pressures. However, in the case of bromoform, the C-Br bonds are significantly weaker; therefore, these atoms can be removed even in a single step via multiphoton absorption. The rotational temperature of CH(A) radicals generated from methanol decreased rapidly in the 30-55 ns time period from 2770 ± 80 to 1530 ± 50 K. The vibrational temperature increased from 3530 ± 450 to 9810 ± 760 K in the 30-80 ns time period and then started to decrease (the average temperatures were Trot = 910 ± 20 K and Tvib = 7490 ± 340 K at 100 ns). This initial increase of Tvib is thought to be the result of electron collision with the CH radicals. The high temperatures of the fragment may indicate the roaming reaction associated with the Coulomb explosion of the parent molecule. We demonstrated that CH(A) radicals can be produced from both organic compounds, and the step-scan technique is ideal for the characterization of their time-resolved spectra using the 100 kHz high repetition rate near-infrared femtosecond laser pulses. The FT/UV-vis step-scan technique can detect neutral species directly with high spectral and time resolution, thus it is a complementary technique to the experiments utilizing ion detection schemes, such as velocity map imaging.

Rotational resonances in the H2CO roaming reaction are revealed by detailed correlations.

Since its discovery 16 years ago, roaming has become a ubiquitous mechanism in molecular photochemistry. Its general features are now understood, but little detail is known about how the potential energy surface (PES) determines reaction outcomes. We performed detailed experiments on formaldehyde (H2CO) photodissociation and determined fully correlated quantum state distributions of the molecular hydrogen and carbon monoxide products. These experiments reveal previously undetected bimodal carbon monoxide rotational distributions. Insights from classical trajectory calculations demonstrate that these features arise from resonances as the PES directs the reaction into cis and trans O-C-H···H critical geometries, which produce rebound and stripping mechanisms, respectively. These subtle and pervasive effects demonstrate additional complexity in this prototypical roaming reaction, which we expect to be general. They also provide detailed benchmarks for predictive theories of roaming.

Formation of CN Radical from Nitrogen and Carbon Condensation and from Photodissociation in Femtosecond Laser-Induced Plasmas: Time-Resolved FT-UV-Vis Spectroscopic Study of the Violet Emission of CN Radical.

Exploring the formation of diatomic radicals in femtosecond plasmas is important to establish the most dominant kinetic pathways following ionization and dissociation of small molecules. In this work, cyano radical formation has been studied from bromoform, acetonitrile, and methanol in nitrogen and argon plasmas created with a focused femtosecond laser beam operating at 100 kHz repetition rate and 1030 nm wavelength with 43 fs pulse length and 250 μJ pulse energy. Time-resolved Fourier transform fluorescence spectroscopy was applied in the ultraviolet-visible (UV-vis) spectral range for the characterization of the rotational and vibrational temperatures of the CN(B) radicals via fitting the experimental data. The high repetition rate of the laser allows efficient coupling with the step-scan Fourier transform spectroscopy method. Coulomb explosion at the very high intensity (∼1016 W/cm2) resulted in the formation of nascent atoms, ions, and electrons. The condensation reactions of carbon and reactive nitrogen species resulted in the formation of CN(B2Σ+) radicals and C2(d3Πg) dicarbon molecules/radicals. The CN(B) radicals were formed at the highest concentration in the case of bromoform because the weak carbon-bromine bonds resulted in reactive carbon atoms and CH radicals, which are reactive precursors for the CN(B) radical formation. In the case of acetonitrile, immediate production of CN(B) is observed with nanosecond resolution, which suggests that the CN is formed either via photodetachment or via roaming reaction associated with the Coulomb explosion of the parent molecule. The nascent rotational temperature was very high (∼6000-8500 K) and rapidly decreased in all instances within 40 ns with bromoform and acetonitrile. The highest vibrational temperature (∼7800 K) was observed in an acetonitrile/Ar mixture that decreased in about 30 ns and then increased in the observed time window. The vibrational temperature increased in all samples between 30 and 200 ns. The time dependence of fluorescence is described with a monoexponential decay in the case of acetonitrile/Ar and with biexponential decays in all other instances in the 0-250 mbar total pressure range. The shorter time constant is close to the radiative lifetime of CN(B) emission (∼60-80 ns), which can be attributed to the CN(B) radicals produced in the first few collisions at lower pressures. The longer CN(B) emission is from CN(B) created by slower chemical reactions involving carbon atoms, C2 radicals, and reactive nitrogen-containing species.

Roaming Reactions and Dynamics in the van der Waals Region.

Roaming reactions were first clearly identified in photodissociation of formaldehyde 15 years ago, and roaming dynamics are now recognized as a universal aspect of chemical reactivity. These reactions typically involve frustrated near-dissociation of a quasibound system to radical fragments, followed by reorientation at long range and intramolecular abstraction. The consequences can be unexpected formation of molecular products, depletion of the radical pool in chemical systems, and formation of products with unusual internal state distributions. In this review, I examine some current aspects of roaming reactions with an emphasis on experimental results, focusing on possible quantum effects in roaming and roaming dynamics in bimolecular systems. These considerations lead to a more inclusive definition of roaming reactions as those for which key dynamics take place at long range.

Rate coefficients of roaming reaction H+MgH using ring polymer molecular dynamics

The ring-polymer molecular dynamics (RPMD) was used to calculate the thermal rate coefficients of the multi-channel roaming reaction H+MgH→Mg+H2. Two reaction channels, tight and roaming, are explicitly considered. This is a pioneering attempt of exerting RPMD method to multi-channel reactions. With the help of a newly developed optimization-interpolation protocol for preparing the initial structures and adaptive protocol for choosing the force constants, we have successfully obtained the thermal rate coefficients. The results are consistent with those from other theoretical methods, such as variational transition state theory and quantum dynamics. Especially, RPMD results exhibit negative temperature dependence, which is similar to the results from variational transition state theory but different from the ones from ground state quantum dynamics calculations.

Ab Initio Molecular Dynamics Simulation Study on the Stereo Reactions between Atomic Oxygen Anion and Methane.

Ion–molecule reaction between atomic oxygen anion (O−) and methane (CH4) has been systematically investigated employing the on-the-fly ab initio molecular dynamics simulations. Besides the major H-abstraction process as the exothermic reaction studied widely, an endothermic pathway to produce OCH3− and H is also observed in this study. Three typical O− attack modes with reference to the pyramid structure of CH4 fixed in space have been considered. It was found that the internal motions of the radical products are significantly dependent on the O− attack modes. As for the reaction between O− and the thermally vibrating CH4, the major pathway to produce OH− and CH3 is preferred by the direct H-abstraction and the minor pathway to produce H and OCH3− is the roaming reaction via the transient negative ion [HO-CH3]−.

The impact of roaming radicals on the combustion properties of transportation fuels

A systematic investigation on the effects of roaming radical reactions on global combustion properties for transportation fuels is presented. New software was developed that can automatically predict all the possible roaming pathways within a given chemical kinetic mechanism. This novel approach was applied to two mechanisms taken from the literature, one for heptane and one for butanol. Ignition delay times and laminar flame speeds were computed over a broad range of conditions, while testing varying degrees of roaming. As the degree of roaming is increased, the ignition delays increased, consistent with the hypothesis that roaming decreases the reactivity of the system. The percent increase in the ignition delay is strongly temperature dependent, with the largest effect seen in the negative temperature coefficient regime. Outside of this temperature range, the effect of roaming on global combustion properties is small, on the order of a few percent for ignition delays and less than a percent for flame speeds. The software that was used to create the new mechanisms and test the effects of roaming on combustion properties are freely available, with detailed tutorials that will enable it to be applied to fuels other than heptane and butanol.

Zero-point energy conservation in classical trajectory simulations: Application to H2CO.

A new approach for preventing zero-point energy (ZPE) violation in quasi-classical trajectory (QCT) simulations is presented and applied to H2CO "roaming" reactions. Zero-point energy may be problematic in roaming reactions because they occur at or near bond dissociation thresholds and these channels may be incorrectly open or closed depending on if, or how, ZPE has been treated. Here we run QCT simulations on a "ZPE-corrected" potential energy surface defined as the sum of the molecular potential energy surface (PES) and the global harmonic ZPE surface. Five different harmonic ZPE estimates are examined with four, on average, giving values within 4 kJ/mol-chemical accuracy-for H2CO. The local harmonic ZPE, at arbitrary molecular configurations, is subsequently defined in terms of "projected" Cartesian coordinates and a global ZPE "surface" is constructed using Shepard interpolation. This, combined with a second-order modified Shepard interpolated PES, V, allows us to construct a proof-of-concept ZPE-corrected PES for H2CO, V eff, at no additional computational cost to the PES itself. Both V and V eff are used to model product state distributions from the H + HCO → H2 + CO abstraction reaction, which are shown to reproduce the literature roaming product state distributions. Our ZPE-corrected PES allows all trajectories to be analysed, whereas, in previous simulations, a significant proportion was discarded because of ZPE violation. We find ZPE has little effect on product rotational distributions, validating previous QCT simulations. Running trajectories on V, however, shifts the product kinetic energy release to higher energy than on V eff and classical simulations of kinetic energy release should therefore be viewed with caution.

The phase space geometry underlying roaming reaction dynamics

Recent studies have found an unusual way of dissociation in formaldehyde. It can be characterized by a hydrogen atom that separates from the molecule, but instead of dissociating immediately it roams around the molecule for a considerable amount of time and extracts another hydrogen atom from the molecule prior to dissociation. This phenomenon has been coined roaming and has since been reported in the dissociation of a number of other molecules. In this paper we investigate roaming in Chesnavich’s hbox {CH}_4^+ model. During dissociation the free hydrogen must pass through three phase space bottleneck for the classical motion, that can be shown to exist due to unstable periodic orbits. None of these orbits is associated with saddle points of the potential energy surface and hence related to transition states in the usual sense. We explain how the intricate phase space geometry influences the shape and intersections of invariant manifolds that form separatrices, and establish the impact of these phase space structures on residence times and rotation numbers. Ultimately we use this knowledge to attribute the roaming phenomenon to particular heteroclinic intersections.

Thermal Decomposition of Phosgene and Diphosgene.

Phosgene (COCl2) is a toxic compound used or formed in a wide range of applications. The understanding of its thermal decomposition for destruction processes or in the event of accidental fire of stored reserves is a major safety issue. In this study, a detailed chemical kinetic model for the thermal decomposition and combustion of phosgene and diphosgene is proposed for the first time. A large number of thermo-kinetic parameters were calculated using quantum chemistry and reaction rate theory. The model was validated against experimental pyrolysis data from the literature. It is predicted that the degradation of diphosgene is mainly ruled by a pericyclic reaction producing two molecules of phosgene and, to a lesser extent, by a roaming radical reaction yielding CO2 and CCl4. Phosgene is much more stable than diphosgene under high-temperature conditions, and its decomposition starts at higher temperatures. Decomposition products are CO and Cl2. An equimolar mixture of the latter molecules can be considered as a surrogate of phosgene from the kinetic point of view, but the important endothermic effect of the decomposition reaction can lead to different behaviors, for instance, in the case of autoignition under high pressure and high temperature.

Products from the Oxidation of n-Butane from 298 to 735 K Using Either Cl Atom or Thermal Initiation: Formation of Acetone and Acetic Acid-Possible Roaming Reactions?

The oxidation of 2-butyl radicals (and to a lesser extent 1-butyl radicals) has been studied over the temperature range of 298-735 K. The reaction of Cl atoms (formed by 360 nm irradiation of Cl2) with n-butane generated the 2-butyl radicals in mixtures of n-C4H10, O2, and Cl2 at temperatures below 600 K. Above 600 K, 2-butyl radicals were produced by thermal combustion reactions in the absence of chlorine. The yields of the products were measured by gas chromatography using a flame ionization detector. Major products quantified include acetone, acetic acid, acetaldehyde, butanone, 2-butanol, butanal, 1- and 2- chlorobutane, 1-butene, trans-2-butene, and cis-2-butene. At 298 K, the major oxygenated products are those expected from bimolecular reactions of 2-butylperoxy radicals (butanone, 2-butanol, and acetaldehyde). As the temperature rises to 390 K, the butanone decreases while acetaldehyde increases because of the increased rate of 2-butoxy radical decomposition. Acetone and acetic acid first appear in significant yield near 400 K, and these species rise slowly at first and then sharply, peaking near 525 K at yields of ∼25 and ∼20 mol %, respectively. In the same temperature range (400-525 K), butanone, acetaldehyde, and 2-butanol decrease rapidly. This suggests that acetone and acetic acid may be formed by previously unknown reaction channels of the 2-butylperoxy radical, which are in competition with those that lead to butanone, acetaldehyde, and 2-butanol. Above 570 K, the yields of acetone and acetic acid fall rapidly as the yields of the butenes rise. Experiments varying the Cl atom density, which in turn controls the entire radical pool density, were performed in the temperature range of 410-440 K. Decreasing the Cl atom density increased the yields of acetone and acetic acid while the yields of butanone, acetaldehyde, and 2-butanol decreased. This is consistent with the formation of acetone and acetic acid by unimolecular decomposition channels of the 2-butylperoxy radical, which are in competition with the bimolecular channels that form butanone, acetaldehyde, and 2-butanol. Such unimolecular decomposition channels would be unlikely to proceed through conventional transition states because those states would be very constrained. Therefore, the possibility that these decomposition channels proceed via roaming should be considered. In addition, we investigated and were unable to fit our data trends by a simplified ketohydroperoxide mechanism.

What is special about how roaming chemical reactions traverse their potential surfaces? Differences in geodesic paths between roaming and non-roaming events.

With the notable exception of some illustrative two-degree-of-freedom models whose surprising classical dynamics has been worked out in detail, theories of roaming have largely bypassed the issue of when and why the counterintuitive phenomenon of roaming occurs. We propose that a useful way to begin to address these issues is to look for the geodesic (most efficient) pathways through the potential surfaces of candidate systems. Although roaming manifests itself in an unusual behavior at asymptotic geometries, we found in the case of formaldehyde dissociation that it was the pathways traversing the parts of the potential surface corresponding to highly vibrationally excited reactants that were the most revealing. An examination of the geodesics for roaming pathways in this region finds that they are much less tightly defined than the geodesics in that same region that lead directly to dissociation (whether into closed-shell products or into radical products). Thus, the broader set of options available to the roaming channel gives it an entropic advantage over more conventional reaction channels. These observations suggest that what leads to roaming in other systems may be less the presence of a localized "roaming transition state," than the existence of an entire region of the potential surface conducive to multiple equivalent pathways.