The O( ³ P) + C ₂ H ₄ reaction, of importance in combustion and atmospheric chemistry, stands out as a paradigm reaction involving triplet- and singlet-state potential energy surfaces (PESs) interconnected by intersystem crossing (ISC). This reaction poses challenges for theory and experiments owing to the ruggedness and high dimensionality of these potentials, as well as the long lifetimes of the collision complexes. Primary products from five competing channels (H + CH ₂ CHO, H + CH ₃ CO, H ₂ + CH ₂ CO, CH ₃ + HCO, CH ₂ + CH ₂ O) and branching ratios (BRs) are determined in crossed molecular beam experiments with soft electron-ionization mass-spectrometric detection at a collision energy of 8.4 kcal/mol. As some of the observed products can only be formed via ISC from triplet to singlet PESs, from the product BRs the extent of ISC is inferred. A new full-dimensional PES for the triplet state as well as spin-orbit coupling to the singlet PES are reported, and roughly half a million surface hopping trajectories are run on the coupled singlet-triplet PESs to compare with the experimental BRs and differential cross-sections. Both theory and experiment find almost equal contributions from the two PESs to the reaction, posing the question of how important is it to consider the ISC as one of the nonadiabatic effects for this and similar systems involved in combustion chemistry. Detailed comparisons at the level of angular and translational energy distributions between theory and experiment are presented for the two primary channel products, CH ₃ + HCO and H + CH ₂ CHO. The agreement between experimental and theoretical functions is excellent, implying that theory has reached the capability of describing complex multichannel nonadiabatic reactions.

We solve the time-dependent Schr\"odinger equation for atomic hydrogen in an intense field using spherical coordinates with a radial grid and a spherical harmonic basis for the angular part. We present the high-order harmonic spectra based on three different forms, the dipole, dipole velocity, and acceleration forms, and two gauges, the length and velocity gauges. The relationships among the harmonic phases obtained from the Fourier transform of the three forms are discussed in detail. Although quantum mechanics is gauge invariant and the length and velocity gauges should give identical results, the two gauges present different computation efficiencies, which reflects the different behavior in terms of characteristics of the physical couplings acting in the two gauges. In order to obtain convergence, more angular momentum states are required in the length gauge, while more grid points are required in the velocity gauge. At lower laser intensity, the calculation in the length gauge is faster than that in the velocity gauge, while at high laser intensity, the calculation in the velocity gauge is more efficient. The velocity gauge is also expected to be more efficient in higher-dimensional calculations.

The reaction of O(³P) with C₂H₄, 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 + CH₂CHO, H + CH₃CO, CH₃ + HCO, CH₂ + H₂CO, and H₂ + CH₂CO. 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(³P) + C₂H₄ 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 + CH₂CHO, CH₃ + HCO, and CH₂ + H₂CO. 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.

The diabatic photodissociation and photoionization processes of the NaI molecule are studied theoretically using the quantum wave packet method. A pump laser pulse is used to prepare a dissociation wave packet that propagates through both the ionic channel (NaI→Na++I−) and the covalent channel (NaI→Na+I). A Stark pulse is used to control the diabatic dissociation dynamics and a probe pulse is employed to ionize the products from the two channels. Based on the first order nonresonant nonperturbative dynamic Stark effect, the dissociation probabilities and the branching ratio of the products from the two channels can be controlled. Moreover the final photoelectron kinetic energy distribution can also be affected by the Stark pulse. The influences of the delay time, intensity, frequency, and carrier-envelope phase of the Stark pulse on the dissociation and ionization dynamics of the NaI molecule are discussed in detail.

Roaming is a novel mechanism in reaction dynamics. It describes an unusual pathway, which can be quite different from the conventional minimum-energy path, leading to products. While roaming has been reported or suggested in a number of unimolecular reactions, it has been rarely reported for bimolecular reactions. Here, we report a high-level computational study of roaming dynamics in the important bimolecular combustion reaction H + C₂H₄ → H₂ + C₂H₃, using a new, high-level machine learning-based potential energy surface. In addition to the complex-mediated roaming mechanism, a non-complex forming roaming mechanism is found. It can be described as a direct inelastic collision where the departing H atom roams and then abstracts an H atom. We denoted this as “collision-induced” roaming. These two roaming mechanisms have different angular distributions; however, both produce highly internally excited C₂H₃. The roaming pathway leads to remarkably different dynamics as compared with the direct abstraction pathway. A clear signature of the roaming mechanism is highly internally excited C₂H₃, which could be observed experimentally.