The reaction of O((3)P) with C(2)H(4), of importance in combustion and atmospheric chemistry, stands out as paradigm reaction involving not only the indicated triplet state potential energy surface (PES) but also an interleaved singlet PES that is coupled to the triplet surface. This reaction poses great challenges for theory and experiment, owing to the ruggedness and high dimensionality of these potentials, as well as the long lifetimes of the collision complexes. Crossed molecular beam (CMB) scattering experiments with soft electron ionization detection are used to disentangle the dynamics of this polyatomic multichannel reaction at a collision energy E(c) of 8.4 kcal∕mol. Five different primary products have been identified and characterized, which correspond to the five exothermic competing channels leading to H + CH(2)CHO, H + CH(3)CO, CH(3) + HCO, CH(2) + H(2)CO, and H(2) + CH(2)CO. These experiments extend our previous CMB work at higher collision energy (E(c) ∼ 13 kcal∕mol) and when the results are combined with the literature branching ratios from kinetics experiments at room temperature (E(c) ∼ 1 kcal∕mol), permit to explore the variation of the branching ratios over a wide range of collision energies. In a synergistic fashion, full-dimensional, QCT surface hopping calculations of the O((3)P) + C(2)H(4) reaction using ab initio PESs for the singlet and triplet states and their coupling, are reported at collision energies corresponding to the CMB and the kinetics ones. Both theory and experiment find almost an equal contribution from the triplet and singlet surfaces to the reaction, as seen from the collision energy dependence of branching ratios of product channels and extent of intersystem crossing (ISC). Further detailed comparisons at the level of angular distributions and translational energy distributions are made between theory and experiment for the three primary radical channel products, H + CH(2)CHO, CH(3) + HCO, and CH(2) + H(2)CO. The very good agreement between theory and experiment indicates that QCT surface-hopping calculations, using reliable coupled multidimensional PESs, can yield accurate dynamical information for polyatomic multichannel reactions in which ISC plays an important role.

In this Perspective we highlight developments in the field of chemical reaction dynamics. Focus is on the advances recently made in the investigation of the dynamics of elementary multichannel radical-molecule and radical-radical reactions, as they have become possible using an improved crossed molecular beam scattering apparatus with universal electron-ionization mass spectrometric detection and time-of-flight analysis. These improvements consist in the implementation of (a) soft ionization detection by tunable low-energy electrons which has permitted us to reduce interfering signals originating from dissociative ionization processes, usually representing a major complication, (b) different beam crossing-angle set-ups which have permitted us to extend the range of collision energies over which a reaction can be studied, from very low (a few kJ mol(-1), as of interest in astrochemistry or planetary atmospheric chemistry) to quite high energies (several tens of kJ mol(-1), as of interest in high temperature combustion systems), and (c) continuous supersonic sources for producing a wide variety of atomic and molecular radical reactant beams. Exploiting these new features it has become possible to tackle the dynamics of a variety of polyatomic multichannel reactions, such as those occurring in many environments ranging from combustion and plasmas to terrestrial/planetary atmospheres and interstellar clouds. By measuring product angular and velocity distributions, after having suppressed or mitigated, when needed, the problem of dissociative ionization of interfering species (reactants, products, background gases) by soft ionization detection, essentially all primary reaction products can be identified, the dynamics of each reaction channel characterized, and the branching ratios determined as a function of collision energy. In general this information, besides being of fundamental relevance, is required for a predictive description of the chemistry of these environments via computer models. Examples are taken from recent on-going work (partly published) on the reactions of atomic oxygen with acetylene, ethylene and allyl radical, of great importance in combustion. A reaction of relevance in interstellar chemistry, as that of atomic carbon with acetylene, is also discussed briefly. Comparison with theoretical results is made wherever possible, both at the level of electronic structure calculations of the potential energy surfaces and dynamical computations. Recent complementary CMB work as well as kinetic work exploiting soft photo-ionization with synchrotron radiation are noted. The examples illustrated in this article demonstrate that the type of dynamical results now obtainable on polyatomic multichannel radical-molecule and radical-radical reactions might well complement reaction kinetics experiments and hence contribute to bridging the gap between microscopic reaction dynamics and thermal reaction kinetics, enhancing significantly our basic knowledge of chemical reactivity and understanding of the elementary rea...

The dynamics of the C + C2H2 reaction has been investigated using two crossed molecular beam apparatus of different concepts. Differential cross sections have been obtained for the C(3PJ) + C2H2(X1sigmag+) --> l/c-C3H + H(2S1/2) reaction in experiments conducted with pulsed supersonic beams and variable beam crossing angle configuration at two relative translational energies ET = 0.80 and 3.5 kJ mol(-1). H(2S1/2) atoms were detected by time-of-flight mass spectrometry with sequential excitation to the 2PJ(o) state using a laser beam tuned at the Lyman-alpha transition around 121.567 nm and ionisation by a second laser beam at 364.7 nm. Doppler-Fizeau spectra of the H atoms were recorded with the Lyman-alpha laser beam parallel to the relative velocity vector of the reagents. These spectra could be fitted using a forward convolution process including two contributions. The recoil energy distribution functions of both contributions were taken as statistical, with total energies corresponding to a reaction exoergicity deltaH0(o) = -11 kJ mol(-1) for the major one, assigned to the c-C3H + H path, and -1.5 kJ mol(-1) for the minor one, assigned to the l-C3H + H path. The angular distribution was taken as also statistical (uniform) for the minor contribution but somewhat backward peaked for the major one. Differential cross sections have been obtained for the three energetically allowed and competitive C(3PJ) + C2H2(X1sigmag+) --> l/c-C3H + H(2S1/2) and C(3PJ) + C2H2(X1sigmag+) --> C3(X1sigmag+) + H2(X1sigmag+) reaction channels in experiments conducted with supersonic continuous beams under 45 degrees crossing angle configuration using "soft" electron-ionisation mass spectrometry time-of-flight detection at ET = 3.5 and 18.5 kJ mol(-1). From measurements of angular and time-of-flight distributions at the mass-to-charge ratios m/z = 37 and 36, product angular and translational energy distributions have been determined in the centre-of-mass system for both linear- and cyclic-C3H isomer formation as well as for C3 production. The variations of the dynamics and product branching ratios with collision energy have been characterized. The ratios c-C3H/l-C3H and C3/C3H from the C(3P) reactions have been both found to decrease with increasing ET. Formation of C3(X1sigmag+) from the C(3P) reaction has been rationalized in terms of intersystem crossing between triplet and singlet C3H2 potential energy surfaces. There is good agreement between the results at ET = 3.5 kJ mol(-1) obtained with the two different crossed molecular beam techniques for the C(3PJ) + C2H2(X1sigmag+) --> l/c-C3H + H(2S1/2) channels. An estimate of the exoergicity of the C(3PJ) + C2H2(X1sigmag+) --> c-C3H + H (2S1/2) pathway from the extent of the translational energy release corroborates the value of deltaH0(o) = -11 kJ mol(-1) obtained from the Doppler-Fizeau measurements. The overall results have been discussed in the light of the available theoretical information on the relevant triplet and singlet C3H2 potential energy surfaces, and compared with the ...

A detailed investigation of the dynamics of the reactions of ground- and excited-state carbon atoms, C(3P) and C(1D), with acetylene is reported over a wide collision energy range (3.6-49.1 kJ mol-1) using the crossed molecular beam (CMB) scattering technique with electron ionization mass spectrometric detection and time-of-flight (TOF) analysis. We have exploited the capability of (a) generating continuous intense supersonic beams of C(3P, 1D), (b) crossing the two reactant beams at different intersection angles (45, 90, and 135 degrees ) to attain a wide range of collision energies, and (c) tuning the energy of the ionizing electrons to low values (soft ionization) to suppress interferences from dissociative ionization processes. From angular and TOF distribution measurements of products at m/z=37 and 36, the primary reaction products of the C(3P) and C(1D) reactions with C2H2 have been identified to be cyclic (c)-C3H + H, linear (l)-C3H + H, and C3 + H2. From the data analysis, product angular and translational energy distributions in the center-of-mass (CM) system for both the linear and cyclic C3H isomers as well as the C3 product from C(3P) and for l/c-C3H and C3 from C(1D) have been derived as a function of collision energy from 3.6 to 49.1 kJ mol-1. The cyclic/linear C3H ratio and the C3/(C3 + c/l-C3H) branching ratios for the C(3P) reaction have been determined as a function of collision energy. The present findings have been compared with those from previous CMB studies using pulsed beams; here, a marked contrast is noted in the CM angular distributions for both C3H- and C3-forming channels from C(3P) and their trend with collision energy. Consequently, the interpretation of the reaction dynamics derived in the present work contradicts that previously proposed from the pulsed CMB studies. The results have been discussed in the light of the available theoretical information on the relevant triplet and singlet C3H2 ab initio potential energy surfaces (PESs). In particular, the branching ratios for the C(3P) + C2H2 reaction have been compared with the available theoretical predictions (approximate quantum scattering calculations and quasiclassical trajectory calculations on ab initio triplet PESs and, very recent, statistical calculations on ab initio triplet PESs as well as on ab initio triplet/singlet PESs including nonadiabatic effects, that is, intersystem crossing). While the experimental branching ratios have been corroborated by the statistical predictions, strong disagreement has been found with the results of the dynamical calculations. The astrophysical implications of the present results have been noted.

We report on the determination of primary products and their branching ratios for the combustion relevant O(3P)+allene reaction by the crossed molecular beams method with soft electron-ionization mass-spectrometric detection at a collision energy of 39.3 kJ/mol. We have explored the reaction dynamics of the open channels leading to C2H4+CO, C2H2+H2CO, C2H3+HCO, CH2CCHO+H, and CH2CO+CH2. Because some of the observed products can only be formed via intersystem crossing (ISC) from triplet to singlet potential energy surfaces, from the product branching ratios we have inferred the extent of ISC. The conclusion is that the O(3P)+allene reaction proceeds mostly (>90%) via ISC. This observation poses the question of how important it is to consider nonadiabatic effects for this and other similar systems involved in combustion chemistry. Another important conclusion is that the interaction of atomic oxygen with allene breaks apart the three-carbon atom chain, mostly producing CO and ethylene.