The Value of Different Experimental Observables: A Transient Absorption Study of the Ultraviolet Excitation Dynamics Operating in Nitrobenzene.

Excess energy redistribution dynamics operating in nitrobenzene under hexane and isopropanol solvation were investigated using ultrafast transient absorption spectroscopy (TAS) with a 267 nm pump and a 340-750 nm white light continuum probe. The use of a nonpolar hexane solvent provides a proxy to the gas-phase environment, and the findings are directly compared with a recent time-resolved photoelectron imaging (TRPEI) study on nitrobenzene using the same excitation wavelength [L. Saalbach et al., J. Phys. Chem. A 2021, 125, 7174-7184]. Of note is the observation of a 1/e lifetime of 3.5-6.7 ps in the TAS data that was absent in the TRPEI measurements. This is interpreted as a dynamical signature of the T2 state in nitrobenzene─analogous to observations in the related nitronaphthalene system, and additionally supported by previous quantum chemistry calculations. The discrepancy between the TAS and TRPEI measurements is discussed, with the overall findings providing an example of how different spectroscopic techniques can exhibit varying sensitivity to specific steps along the overall reaction coordinate connecting reactants to photoproducts.

Inelastic scattering of OH from a liquid PFPE surface: Resolution of correlated speed and angular distributions.

Inelastic collisions of OH with an inert liquid perfluoropolyether (PFPE) surface have been studied experimentally. A pulsed molecular beam of OH with a kinetic energy distribution peaking at 35 kJ mol-1 was directed at a continually refreshed PFPE surface. OH molecules were detected state-selectively with spatial and temporal resolution by pulsed, planar laser-induced fluorescence. The scattered speed distributions were confirmed to be strongly superthermal, regardless of the incidence angle (0° or 45°). Angular scattering distributions were measured for the first time; their reliability was confirmed through extensive Monte Carlo simulations of experimental averaging effects, described in Paper II [A. G. Knight et al., J. Chem. Phys. 158, 244705 (2023)]. The distributions depend markedly on the incidence angle and are correlated with scattered OH speed, consistent with predominantly impulsive scattering. For 45° incidence, the angular distributions are distinctly asymmetric to the specular side but peak at sub-specular angles. This, along with the breadth of the distributions, is incompatible with scattering from a surface that is flat on a molecular scale. New molecular dynamics simulations corroborate the roughness of the PFPE surface. A subtle but unexpected systematic dependence of the angular distribution on the OH rotational state was found, which may be dynamical in origin. The OH angular distributions are similar to those for kinematically similar Ne scattering from PFPE and hence not strongly perturbed by OH being a linear rotor. The results here are broadly compatible with prior predictions from independent quasiclassical trajectory simulations of OH scattering from a model-fluorinated self-assembled monolayer surface.

Surface Structure of Alkyl/Fluoroalkylimidazolium Ionic-Liquid Mixtures.

The gas-liquid interface of ionic liquids (ILs) is critically important in many applications, for example, in supported IL phase (SILP) catalysis. Methods to investigate the interfacial structure in these systems will allow their performance to be improved in a rational way. In this study, reactive-atom scattering (RAS), surface tension measurements, and molecular dynamics (MD) simulations were used to study the vacuum interface of mixtures of partially fluorinated and normal alkyl ILs. The underlying aim was to understand whether fluorinated IL ions could be used as additives to modify the surface structure of one of the most widely used families of alkyl ILs. The series of ILs 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][Tf2N]) with n = 4-12 were mixed with a fixed-length, semiperfluorinated analogue (1H,1H,2H,2H-perfluorooctyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mimF13][Tf2N]), forming [Cnmim](1-x)[C8mimF13]x[Tf2N] mixtures, where x is the bulk mole fraction of the fluorinated component. The RAS-LIF method combined O-atom projectiles with laser-induced fluorescence (LIF) detection of the product OH as a measure of surface exposure of the alkyl chains. For [C8mim](1-x)[C8mimF13]x[Tf2N] mixtures, RAS-LIF OH yields are below those expected from stoichiometry. There are quantitatively consistent negative deviations from linearity of the surface tension. Both results imply that the lower-surface-tension fluoroalkyl material dominates the surface. A similar deficit is found for alkyl chain lengths n = 4, 6, 8, and 12 and for all (nonzero) x investigated by RAS-LIF. Accessible-surface-area (ASA) analyses of the MD simulations for [Cnmim](1-x)[C8mimF13]x[Tf2N] mixtures qualitatively reproduce the same primary effect of fluoro-chain predominance of the surface over most of the range of n. However, there are significant quantitative discrepancies between MD ASA predictions and experiment relating to the strength of any n-dependence of the relative alkyl coverage at fixed x, and on the x-dependence at fixed n. These discrepancies are discussed in the context of detailed examinations of the surface structures predicted in the MD simulations. Potential explanations, beyond experimental artifacts, include inadequacies in the classical force fields used in the MD simulations or the inability of simple ASA algorithms to capture dynamical factors that influence RAS-LIF yields.

Vibrational Excitation of Both Products of the Reaction of CN Radicals with Acetone in Solution.

Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands: "free" (uncomplexed) CN radicals, and "solvated" CN radicals that are complexed with solvent molecules. The lifetimes of the free CN radicals are limited to a few picoseconds following their photolytic production because of geminate recombination to ICN and INC, complexation with CDCl3 molecules, and reaction with acetone. The acetone reaction occurs with a rate coefficient of (8.0 ± 0.5) × 10(10) M(-1) s(-1) and transient vibrational spectra in the C═N and C═O stretching regions reveal that both the nascent HCN and 2-oxopropyl (CH3C(O)CH2) radical products are vibrationally excited. The rate coefficient for the reaction of solvated CN with acetone is 40 times slower than for free CN, with a rate coefficient of (2.0 ± 0.9) × 10(9) M(-1) s(-1) obtained from the rise in the HCN product v1(C═N stretch) IR absorption band. Evidence is also presented for CN complexes with acetone that are more strongly bound than the CN-CDCl3 complexes because of CN interactions with the carbonyl group. The rates of reactions of these more strongly associated radicals are slower still.

Differential and integral cross sections for the rotationally inelastic scattering of methyl radicals with H2 and D2.

Comparisons are presented of experimental and theoretical studies of the rotationally inelastic scattering of CD3 radicals with H2 and D2 collision partners at respective collision energies of 680 ± 75 and 640 ± 60 cm(-1). Close-coupling quantum-mechanical calculations performed using a newly constructed ab initio potential energy surface (PES) provide initial-to-final CD3 rotational level (n, k → n', k') integral and differential cross sections (ICSs and DCSs). The DCSs are compared with crossed molecular beam and velocity map imaging measurements of angular scattering distributions, which serve as a critical test of the accuracy of the new PES. In general, there is very good agreement between the experimental measurements and the calculations. The DCSs for CD3 scattering from both H2 and D2 peak in the forward hemisphere for n' = 2-4 and shift more to sideways and backward scattering for n' = 5. For n' = 6-8, the DCSs are dominated by backward scattering. DCSs for a particular CD3 n → n' transition have a similar angular dependence with either D2 or H2 as collision partner. Any differences between DCSs or ICSs can be attributed to mass effects because the PES is unchanged for CD3-H2 and CD3-D2 collisions. Further comparisons are drawn between the CD3-D2 scattering and results for CD3-He presented in our recent paper [O. Tkác, A. G. Sage, S. J. Greaves, A. J. Orr-Ewing, P. J. Dagdigian, Q. Ma, and M. H. Alexander, Chem. Sci. 4, 4199 (2013)]. These systems have the same reduced mass, but are governed by different PESs.

Dynamics of photodissociation of XeF2 in organic solvents.

Transient electronic absorption measurements with 1 ps time resolution follow XeF2 photoproducts in acetonitrile and chlorinated solvents. Ultraviolet light near 266 nm promptly breaks one Xe-F bond, and probe light covering 320-700 nm monitors the products. Some of the cleaved F atoms remain in close proximity to an XeF fragment and perturb the electronic states of XeF. The time evolution of a perturbed spectral feature is used to monitor the FXe-F complex population, which decays in less than 5 ps. Decay can occur through geminate recombination, diffusive separation or reaction of the complex with the solvent.

Ultrafast energy flow in the wake of solution-phase bimolecular reactions.

Vibrational energy flow into reactants, and out of products, plays a key role in chemical reactivity, so understanding the microscopic detail of the pathways and rates associated with this phenomenon is of considerable interest. Here, we use molecular dynamics simulations to model the vibrational relaxation that occurs during the reaction CN + c-C(6)H(12) â†’ HCN + c-C(6)H(11) in CH(2)Cl(2), which produces vibrationally hot HCN. The calculations reproduce the observed energy distribution, and show that HCN relaxation follows multiple timescales. Initial rapid decay occurs through energy transfer to the cyclohexyl co-product within the solvent cage, and slower relaxation follows once the products diffuse apart. Re-analysis of the ultrafast experimental data also provides evidence for the dual timescales. These results, which represent a formal violation of conventional linear response theory, provide a detailed picture of the interplay between fluctuations in organic solvent structure and thermal solution-phase chemistry.

Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution.

The dynamics of reactions of CN radicals with cyclohexane, d(12)-cyclohexane, and tetramethylsilane have been studied in solutions of chloroform, dichloromethane, and the deuterated variants of these solvents using ultraviolet photolysis of ICN to initiate a reaction. The H(D)-atom abstraction reactions produce HCN (DCN) that is probed in absorption with sub-picosecond time resolution using ∼500 cm(-1) bandwidth infrared (IR) pulses in the spectral regions corresponding to C-H (or C-D) and C≡N stretching mode fundamental and hot bands. Equivalent IR spectra were obtained for the reactions of CN radicals with the pure solvents. In all cases, the reaction products are formed at early times with a strong propensity for vibrational excitation of the C-H (or C-D) stretching (v(3)) and H-C-N (D-C-N) bending (v(2)) modes, and for DCN products there is also evidence of vibrational excitation of the v(1) mode, which involves stretching of the C≡N bond. The vibrationally excited products relax to the ground vibrational level of HCN (DCN) with time constants of ∼130-270 ps (depending on molecule and solvent), and the majority of the HCN (DCN) in this ground level is formed by vibrational relaxation, instead of directly from the chemical reaction. The time-dependence of reactive production of HCN (DCN) and vibrational relaxation is analysed using a vibrationally quantum-state specific kinetic model. The experimental outcomes are indicative of dynamics of exothermic reactions over an energy surface with an early transition state. Although the presence of the chlorinated solvent may reduce the extent of vibrational excitation of the nascent products, the early-time chemical reaction dynamics in these liquid solvents are deduced to be very similar to those for isolated collisions in the gas phase. The transient IR spectra show additional spectroscopic absorption features centered at 2037 cm(-1) and 2065 cm(-1) (in CHCl(3)) that are assigned, respectively, to CN-solvent complexes and recombination of I atoms with CN radicals to form INC molecules. These products build up rapidly, with respective time constants of 8-26 and 11-22 ps. A further, slower rise in the INC absorption signal (with time constant >500 ps) is attributed to diffusive recombination after escape from the initial solvent cage and accounts for more than 2/3 of the observed INC.

Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution.

Solvent collisions can often mask initial disposition of energy to the products of solution-phase chemical reactions. Here, we show with transient infrared absorption spectra obtained with picosecond time resolution that the nascent HCN products of reaction of CN radicals with cyclohexane in chlorinated organic solvents exhibit preferential excitation of one quantum of the C-H stretching mode and up to two quanta of the bending mode. On time scales of approximately 100 to 300 picoseconds, the HCN products undergo relaxation to the vibrational ground state by coupling to the solvent bath. Comparison with reactions of CN radicals with alkanes in the gas phase, known to produce HCN with greater C-H stretch and bending mode excitation (up to two and approximately six quanta, respectively), indicates partial damping of the nascent product vibrational motion by the solvent. The transient infrared spectra therefore probe solvent-induced modifications to the reaction free energy surface and chemical dynamics.

Chemical Reaction Dynamics in Liquid Solutions.

The dynamics of bimolecular chemical reactions can be examined in liquid solutions using infrared absorption spectroscopy with picosecond time resolution. On such short time scales, the transient absorption spectra reveal vibrational mode and quantum-state-specific energy disposal, followed by vibrational relaxation as the energy is dissipated to the surrounding solvent. Comparison with energy disposal measurements for gas-phase reactions under single-collision conditions offers direct insights into the modification of the energy landscape and the nuclear dynamics in the presence of the solvent. The reactions of CN radicals with organic molecules in chlorinated solvents exemplify the dynamical information that can be obtained. The potential to extend such experiments to a range of reactions and solvents is discussed.

Velocity map imaging the dynamics of the reactions of Cl atoms with neopentane and tetramethylsilane.

The reactions of ground state Cl((2)P(3/2)) atoms with neopentane and tetramethylsilane have been studied at collision energies of 7.9+/-2.0 and 8.2+/-2.0 kcal mol(-1), respectively. The nascent HCl(v=0,J) products were probed using resonance enhanced multiphoton ionization spectroscopy combined with velocity map imaging (VMI) to determine the rotational level population distributions, differential cross sections (DCSs), and product translational energy distributions. The outcomes from PHOTOLOC and dual beam methods are compared and are discussed in light of previous studies of the reactions of Cl atoms with other saturated hydrocarbons, including a recent crossed molecular beam and VMI investigation of the reaction of Cl atoms with neopentane [Estillore et al., J. Chem. Phys. 132, 164313 (2010)]. Rotational distributions were observed to be cold, consistent with the reactions proceeding via a transition state with a collinear Cl-H-C moiety. The DCSs for both reactions are forward peaked but show scatter across a broad angular range. Interpretation using a model based on linear dependence of scattering angle on impact parameter indicates that the probability of reaction is approximately constant across all allowed impact parameters. Product translational energy distributions from dual beam experiments have mean values, expressed as fractions of the total available energy, of 0.67 (Cl+neopentane) and 0.64 (Cl+tetramethylsilane) that are consistent with a kinematic model for the reaction in which the translational energy of the reactants is conserved into product translational energy.

Velocity map imaging of the dynamics of bimolecular chemical reactions.

The experimental technique of velocity map imaging (VMI) enables measurements to be made of the dynamics of chemical reactions that are providing unprecedented insights about reactive scattering. This perspective article illustrates how VMI, in combination with crossed-molecular beam, dual-beam or photo-initiated (Photoloc) methods, can reveal correlated information on the vibrational quantum states populated in the two products of a reaction, and the angular scattering of products (the differential cross section) formed in specific rotational and vibrational levels. Reactions studied by VMI techniques are being extended to those of polyatomic molecules or radicals, and of molecular ions. Subtle quantum-mechanical effects in bimolecular reactions can provide distinct signatures in the velocity map images, and are exemplified here by non-adiabatic dynamics on coupled potential energy surfaces, and by experimental evidence for scattering resonances.

Classical trajectory study of the dynamics of the reaction of Cl atoms with ethane.

We present an electronic-structure and dynamics study of the Cl + C2H6 --> HCl + C2H5 reaction. The stationary points of the ground-state potential energy surface have been characterized using various electronic-structure methods and basis sets. Our best calculations, CCSD(T) extrapolated to the complete basis limit, using geometries and harmonic frequencies obtained at the MP2/aug-cc-pVTZ level, are in agreement with the experimental reaction energy. Ab initio information has been used to reparameterize a semiempirical Hamiltonian so that the predictions of the improved Hamiltonian agree with the higher-level calculations in key regions of the potential energy surface. The improved semiempirical Hamiltonian is then used to propagate quasiclassical trajectories. Computed kinetic energy release and scattering angle distributions at a collision energy of approximately 5.5 kcal mol(-1) are in reasonable agreement with experiments, but no evidence was found for the low translational energy HCl products scattered in the backward hemisphere reported in recent experiments.

Vibrational excitation through tug-of-war inelastic collisions.

Vibrationally inelastic scattering is a fundamental collision process that converts some of the kinetic energy of the colliding partners into vibrational excitation(,). The conventional wisdom is that collisions with high impact parameters (where the partners only 'graze' each other) are forward scattered and essentially elastic, whereas collisions with low impact parameters transfer a large amount of energy into vibrations and are mainly back scattered. Here we report experimental observations of exactly the opposite behaviour for the simplest and most studied of all neutral-neutral collisions: we find that the inelastic scattering process H + D(2)(v = 0, j = 0, 2) --> H + D(2)(v' = 3, j' = 0, 2, 4, 6, 8) leads dominantly to forward scattering (v and j respectively refer to the vibrational and rotational quantum numbers of the D(2) molecule). Quasi-classical trajectory calculations show that the vibrational excitation is caused by extension, not compression, of the D-D bond through interaction with the passing H atom. However, the H-D interaction never becomes strong enough for capture of the H atom before it departs with diminished kinetic energy; that is, the inelastic scattering process is essentially a frustrated reaction in which the collision typically excites the outward-going half of the H-D-D symmetric stretch before the H-D(2) complex dissociates. We suggest that this 'tug of war' between H and D(2) is a new mechanism for vibrational excitation that should play a role in all neutral-neutral collisions where strong attraction can develop between the collision partners.

Adiabatic and nonadiabatic dynamics in the CH3(CD3)+HCl reaction.

The scattering dynamics leading to the formation of Cl (2P(3/2)) and Cl* (2P(1/2)) products of the CH(3)+HCl reaction (at a mean collision energy =22.3 kcal mol(-1)) and the Cl (2P(3/2)) products of the CD(3)+HCl reaction (at =19.4 kcal mol(-1)) have been investigated by using photodissociation of CH(3)I and CD(3)I as sources of translationally hot methyl radicals and velocity map imaging of the Cl atom products. Image analysis with a Legendre moment fitting procedure demonstrates that, in all three reactions, the Cl/Cl* products are mostly forward scattered with respect to the HCl in the center-of-mass (c.m.) frame but with a backward scattered component. The distributions of the fraction of the available energy released as translation peak at f(t)=0.31-0.33 for all the reactions, with average values that lie in the range =0.42-0.47. The detailed analysis indicates the importance of collision energy in facilitating the nonadiabatic transitions that lead to Cl* production. The similarities between the c.m.-frame scattering and kinetic energy release distributions for Cl and Cl* channels suggest that the nonadiabatic transitions to a low-lying excited potential energy surface (PES) correlating to Cl* products occur after passage through the transition state region on the ground-state PES. Branching fractions for Cl* are determined to be 0.14+/-0.02 for the CH(3)+HCl reaction and 0.20+/-0.03 for the CD(3)+HCl reaction. The difference cannot be accounted for by changes in collision energy, mass effects, or vibrational excitation of the photolytically generated methyl radical reagents and instead suggests that the low-frequency bending modes of the CD(3)H or CH(4) coproduct are important mediators of the nonadiabatic couplings occurring in this reaction system.

New, unexpected, and dominant mechanisms in the hydrogen exchange reaction.

A quasiclassical trajectory study of the state specific H+D(2)(upsilon = 0,j = 0) --> HD(upsilon' = 0,j' = 0) + D reaction at a collision energy of 1.85 eV (total energy of 2.04 eV) found that the scattering is governed by two unexpected and dominant new mechanisms, and not by direct recoil as is generally assumed. The new mechanisms involve strong interaction with the sloping potential around the conical intersection, an area of the potential energy surface not previously considered to have much effect upon reactive scattering. Initial investigations indicate that more than 50% of reactive scattering could be the result of these new mechanisms at this collision energy. Features in the corresponding quantum mechanical results can be attributed to these new (classical) reaction mechanisms.

A quasiclassical trajectory study of the time-delayed forward scattering in the hydrogen exchange reaction.

The time-delayed forward scattering mechanism recently identified by Althorpe et al. [Nature (London) 416, 67 (2002)] for the H+D(2)(v=0,j=0)-->HD(v(')=3,j(')=0)+D reaction was analyzed by using quasiclassical trajectory (QCT) methodology. The QCT results were found to match the quantum wavepacket snapshots of Althorpe et al., albeit without the quantum scattering effects. Trajectories were analyzed on the fly to investigate the dynamics of the atoms during the reaction. The dominant reaction mechanism progresses from hard collinear impacts, leading to direct recoil, toward glancing impacts. The increased time required for forward scattered trajectories is due to the rotation of the transient HDD complex. Forward scattered trajectories display symmetric stretch vibrations of the transient HDD complex, a signature of the presence of a resonance, or a quantum bottleneck state.

The dynamics of reaction of Cl atoms with tetramethylsilane.

Rotational state distributions and state-selected CM-frame angular distributions were measured for HCl (v' = 0, j') products from the reaction of Cl-atoms with tetramethylsilane (TMS) under single collision conditions at a collision energy, E(coll), of 8.2 +/- 2.0 kcal mol(-1). The internal excitation of these products was very low with only 2% of the total energy available partitioned into HCl rotation. A transition state with a quasi-linear C-H-Cl moiety structure was computed and used to explain this finding. A backward peaking differential cross section was also reported together with a product translational energy (T') distribution with a maximum at T' approximately E(coll). This scattering behaviour is accounted for by reactions proceeding through a tight transition state on a highly skewed potential energy surface, which favours collisions at low impact parameters with a strong kinematic constraint on the internal excitation of the products. The large Arrhenius pre-exponential factor previously reported for this reaction is reconciled with the tight differential scattering observed in our study by considering the large size of the TMS molecule.

Imaging the dynamics of reactions between Cl atoms and the cyclic ethers oxirane and oxetane.

Direct current slice velocity map ion images of the HCl(nu' = 0, J') products from the photoinitiated reactions of ground state Cl atoms with ethane, oxirane (c-C2H4O), and oxetane (c-C3H6O), at respective mean collision energies of 5.5, 6.5, and 7.3 kcal mol-1(-1), were analyzed using a Legendre moment fitting procedure. The experimental method and the fitting technique were tested by comparing the derived center-of-mass (CM) frame angular scattering distribution for the HCl(v' = 0, J' = 1) products from the reaction of Cl + C2H6 with those determined by Suits and co-workers from a crossed molecular beam experiment. For the Cl + c-C2H4O reaction, a broad, forward, and backward peaking CM frame angular distribution of HCl(nu' = 0, J' = 2) products was determined, with an average fraction of the available energy released as product translational energy of f t, equal to 0.52 +/- 0.18. The HCl consumes only 1% of the available energy, and conservation arguments dictate that the radical coproduct is significantly internally excited, corresponding to an average fraction of the available energy of f int(c-C2H3O), equal to 0.47 +/- 0.18. For the reaction of oxetane with Cl atoms, abstraction of H atoms is possible from carbon atoms from positions either alpha or beta to the O atom. The contributions to the reaction from these two H-atom abstraction channels were estimated to be 63 and 37%, consistent with an unbiased propensity for removal of alpha- and beta-H atoms that are present in 2:1 abundance. The angular scatter of products in the CM frame is also broad and forward-backward peaking and is reminiscent of the products of the Cl + CH3OH and CH3OCH3 reactions. The derived mean fraction of the available energy channelled into product translation is f t = 0.54 +/- 0.12 for each of the two abstraction pathways. With only a small amount of energy in the rotation of the HCl(nu' = 0), the remainder is accounted for by excitation of the radical coproduct internal modes, with f int(c-C3H5O) = 0.42 +/- 0.12 for both alpha- and beta-H abstraction. The broad product scattering in the CM frame observed for both reactions of Cl atoms with the cyclic ethers is consistent with reactive collisions over a wide range of impact parameters, as might be expected for barrierless reactions with loose transition states.

Imaging the nonadiabatic dynamics of the CH3 + HCl reaction.

LAB-frame velocity distributions of Cl-atoms produced in the photoinitiated reaction of CH(3) radicals with HCl have been measured for both the ground Cl ((2)P(3/2)) and excited Cl* ((2)P(1/2)) spin-orbit states using a DC slice velocity-map ion imaging technique. The similarity of these distributions, as well as the average internal excitation of methane co-products for both Cl and Cl* pathways, suggest that all the reactive flux proceeds through the same transition state on the ground potential energy surface (PES) and that the couplings which promote nonadiabatic transitions to the excited PES correlating to Cl* occur later in the exit channel, beyond the TS region. The nature of these couplings is discussed in light of initial vibrational excitation of CH(3) radicals as well as previously reported nonadiabatic reactivity in other polyatomic molecule reactions. Furthermore, the scattering of the reaction products, derived using the photoloc method, suggests that at the high collision energy of our experiment (E(coll) = 22.3 kcal mol(-1)), large impact parameter collisions are favoured with a reduced kinematic constraint on the internal excitation of the methane co-product.