Molecular chemisorption at a metal surface is a key step for many processes, such as catalysis, electrochemistry, surface treatment, tribology and friction. Modeling with density functional theory is largely used on these systems. From a detailed comparison with accurate micro-calorimetric data on ten systems (involving ethylene, cyclohexene, benzene, naphthalene, CO, O₂, H₂, methane, ethane), we study the accuracy, for chemisorption on Pt(111), of five exchange–correlation functionals including one generalized gradient approximation functional (PBE) and four functionals that take into account van der Waals interactions (optPBE-vdW, optB86b-vdW, BEEF-vdW, PBE-dDsC). If the functionals used provide very similar geometries and electronic structures, as shown by projected density of states, they give strikingly different results for the adsorption energy of molecules on Pt(111). Among the set of chemisorption data, the lowest mean absolute deviations (MAD) are obtained with the optPBE-vdW and PBE-dDsC functionals (∼0.2 eV) while PBE and optB86b-vdW give twice larger MAD (∼0.45 eV). BEEF-vdW is intermediate with a MAD of 0.33 eV. For laterally π-bound unsaturated hydrocarbons (cyclohexene, benzene, naphthalene) the PBE and the BEEF-vdW functionals are severally under-bound, while optPBE-vdW and PBE-dDsC provide a good match with experiments. Hence both the incorporation of van der Waals dispersive forces and the choice of the exchange functional have a key influence on the chemisorption energy. Vertically bound ethylidyne and CO are in contrast over-bound with all functionals, the best agreement being obtained with BEEF-vdW. None of the selected functionals hence provides a universally accurate treatment of chemisorption energies.

We present an ab initio potential energy surface for the ground electronic state of ozone. It is global, i.e., it covers the three identical $C_{\text{2v}}$ (open) minima, the $D_{\text{3h}}$ (ring) minimum, as well as the $\mathrm{O}{(}^3\mathrm{P)+}{\mathrm{O}}_2{(}^3{\Sigma }_g^{-})$ dissociation threshold. The electronic structure calculations are performed at the multireference configuration interaction level with complete active space self-consistent-field reference functions and correlation consistent polarized quadruple zeta atomic basis functions. Two of the O–O bond distances, $R_1$ and $R_2,$ and the O–O–O bending angle are varied on a regular grid (ca. 5000 points with $R_1{\mathrm{⩾R}}_2\mathrm{).}$ An analytical representation is obtained by a three-dimensional cubic spline. The calculated potential energy surface has a tiny dissociation barrier and a shallow van der Waals minimum in the exit channel. The ring minimum is separated from the three open minima by a high potential barrier and therefore presumably does not influence the low-temperature kinetics. The dissociation energy is reproduced up to 90% of the experimental value. All bound states of nonrotating ozone up to more than 99% of the dissociation energy are calculated using the filter diagonalization technique and employing Jacobi coordinates. The three lowest transition energies for ${}^{\mathrm{16}}{\mathrm{O}}_{\mathrm{3}}$ are 1101.9 cm⁻¹ (1103.14 cm⁻¹), 698.5 cm⁻¹ (700.93 cm⁻¹), and 1043.9 cm⁻¹ (1042.14 cm⁻¹) for the symmetric stretch, the bending, and the antisymmetric stretch modes, respectively; the numbers in parentheses are the experimental values. The root-mean-square error for all measured transition energies for ${}^{16}{\mathrm{O}}_{\mathrm{3}}$ is only 5 cm⁻¹. The comparison is equally favorable for all other isotopomers, for which experimental frequencies are available. The assignment is made in terms of normal modes, despite the observation that with increasing energy an increasing number of states acquires local-mode character. At energies close to the threshold a large fraction of states is still unambiguously assignable, particularly those of the overtone progressions. This is in accord with the existence of stable classical periodic orbits up to very high energies.

▪ Abstract Dynamical studies of the recombination of O and O₂ to form ozone are reviewed. The focus is the intriguing isotope dependence of the recombination rate coefficient as observed by Mauersberger and coworkers in the last decade. The key quantity for understanding of this dependence appears to be the difference of zero-point energies of the two fragmentation channels to which excited ozone can dissociate, i.e., X + YZ ← XYZ^* → XY + Z, where X, Y, and Z stand for the three isotopes of oxygen. Besides the isotope dependence, the variation of the recombination rate coefficient with pressure and temperature is also addressed. Despite the numerous approaches of recent years, the recombination of ozone is far from being satisfactorily explained; there are still several essential questions to be solved by detailed theoretical analysis. We mainly discuss—and critically assess—the results of our own investigations of the ozone kinetics. The work of other research groups is also evaluated.

A new potential energy surface for ozone is developed. It is based on high level ab initio data and includes an accurate description of the barrier region. Full quantum reactive scattering calculations using a coupled channel approach and hyperspherical coordinates are performed on this surface for various isotopic compositions of ozone. Collision lifetimes are obtained over a wide energy range, which gives the spectrum of rovibrational metastable states (scattering resonances). This spectrum is discovered to be very nonstatistical. The spectrum of resonances is dense below the isotopic zero-point-energy threshold and sparse above it. This feature is explained by the opening of additional dissociation channels at higher energies. This behavior is a general quantum mechanical effect that should occur in other triatomic molecules.