Molecular beam experiments are reported for collisions between oxygen molecules. Total integral cross sections have been measured as a function of the collision energy with the control of molecular alignment. The low collision energy (in the thermal and subthermal range) and the high angular resolution permit observation of the “glory” effect, manifestation of quantum-mechanical interference, which allows an accurate probe of intermolecular interactions. This first complete experimental characterization of the interaction yields a ground (singlet) state bond energy of 17.0 ± 0.8 meV for the most stable dimer geometry (the two oxygen molecules lying parallel at a distance of 3.56 ± 0.07 Å). Also the splittings among the singlet, the triplet, and the quintet surfaces are obtained, and a full representation of their angular dependence is reported via a novel harmonic expansion functional form for diatom−diatom interactions. These results indicate that most of the bonding in the dimer comes from van der Waals forces, but chemical (spin−spin) contributions in this open-shell/open-shell system are not negligible (∼15% of the van der Waals component of the interaction).

Exact quantum reactive scattering calculations in the collision energy range 1-250 meV have been carried out for both the isotopic product channels of the title system. The dynamical studies compares an ab initio potential energy surface (PES) recently appeared in the literature (J. Chem. Phys., 2008, 129, 011103) with other phenomenological PESs. Vibrational branching ratios, cross sections and rate constants are presented and compared with molecular beam scattering experiments as well as with chemical kinetics data. In particular, the agreement of the vibrational branching ratios with experimental measurements is improved with respect to previous studies on other PESs, mainly because of the presence of a broad peak in the HF(v' = 3) integral cross section completely absent in the previous simulations. This feature, observed by molecular beam experiments, is the fingerprint of a new reaction mechanism operative in the dynamics described by the new PES. A conjecture for its origin, able to explain many of its characteristic aspects, is analyzed and discussed.

In this paper we present the theoretical concepts and methodology of the hyperquantization algorithm for the three body quantum mechanical problem. Within the framework of the hyperspherical approach to reaction dynamics, we use angular momentum algebra (or its generalization, e.g., including Hahn coefficients which are orthonormal polynomials on a set of grid points which span the interaction region) to compute matrix elements of the Hamiltonian operator parametrically in the hyperradius. The particularly advantageous aspects of the method proposed here is that no integrals are required and the construction of the kinetic energy matrix is simple and universal: salient features are the block tridiagonal structure of the Hamiltonian matrix and a number of symmetry properties. The extremely sparse structure is a further advantage for the diagonalization required to evaluate the adiabatic hyperspherical states as a function of the hyperradius. Numerical implementation is illustrated in the following paper by a specific example.

Systems of orthogonal coordinates for the problem of the motion of three or more particles in classical or in quantum mechanics are considered from the viewpoint of applications to intramolecular dynamics and chemical kinetics. These systems, for which the kinetic energy of relative motion is diagonal, are generated by making extensive use of the concept of kinematic rotations, which act on coordinates of different particles and describe their rearrangements. An explicit representation of these rotations by mass dependent matrices allows to relate different particle couplings in the Jacobi scheme, and to build up alternative systems (such as those based on the Radau–Smith vectors or variants thereof): this makes it possible to obtain coordinates which, while being rigorously orthogonal, may approximate closely the local ones, which are based on actual interparticle distances and are in general nonorthogonal. It is also briefly shown that by defining as variables the parameters describing the kinematic rotations it is possible to obtain nonorthogonal systems of coordinates, which are useful in the treatment of collective modes.

The intermediate and long-range behavior of the three lowest doublet potential energy surfaces for the F(2P j )-H2 and Cl(2P j )-H2 systems has been studied, using a harmonic expansion of the potential, where the dependence on the relative orientation of the half-filled orbital of the open-shell atom and the molecular axis has been given in terms of bipolar spherical harmonics, whereas the coefficients modulate the effect of the variation of the intermolecular distance. The contribution of van der Waals, electrostatic, and charge-transfer interactions to the strength and the intermolecular distance dependence of each radial term are derived from previous molecular beam scattering experiments and from correlation formulas. The latter provide the link of these quantities to basic properties of the interacting partners. Besides describing elastic and inelastic channels, these surfaces also provide accurate information on the entrance channel for reactions.

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We report a study on the behavior with total angular momentum J of several resonances occurring at collision energies below or slightly above the reaction barrier in the F+H2-->HF+H reaction. Resonance positions and widths are extracted from exact time-independent quantum mechanical calculations using the hyperquantization algorithm and Smith's Q-matrix formalism which exploits complete S-matrix information. The results confirm previous work but provide much greater insight. Identification of quasi-bound states responsible for the resonances based on adiabatic models for the long-range atom-molecule interactions both in the entrance and exit channels, is successful except for the feature occurring at the lowest energy, which is found to overlap with an exit-channel resonance for J approximately 7. The two features are analyzed as overlapping resonances and their excellent Lorentzian fits, with well-behaved J-dependences of positions and widths, support the interpretation of the low-energy feature as a resonance to be associated to the triatomic transition state of the reaction. Resonance role on the reactive observables (integral cross sections and angular distributions) is investigated. The mechanism leading to forward scattering in the reactive differential cross section is commented, while the effects on rate constants, as well as the sensitivity of the resonance pattern to modification of the potential energy surface, are fully discussed elsewhere.