The photodissociation of O3 at 266 nm has been studied using velocity mapped ion imaging. We report temperature-dependent vector correlations for the O2(a1Δg, v = 0, j = 18–20) fragments at molecular beam temperatures of 70 K, 115 K, and 170 K. Both the fragment spatial anisotropy and the v-j correlations are found to be increasingly depolarized with increasing beam temperature. At all temperatures, the v-j correlations for the j = 19 state were shown to be reduced compared to those of j = 18 and 20, while no such odd/even rotational state difference was observed for the spatial anisotropy, consistent with previous measurements. We find that temperature-dependent differences in the populations and v-j correlations between the odd and even rotational states can be explained by a Λ-doublet propensity model. Although symmetry conservation should lead to formation of only the A′ Λ-doublet component, and only even rotational states, out-of-plane rotation of the parent molecule breaks the planar symmetry and permits the formation of the A″ Λ-doublet component and odd rotational states. A simple classical model to treat the effect of parent rotation on the v-j correlation and the odd/even rotational population alternation reproduces both the current measurements and previously reported rotational distributions, suggesting that the “odd” behavior originates from a Λ-doublet propensity, and not from a mass independent curve crossing effect, as previously proposed.

We report the rotational state distribution and vector correlations of the O2(a 1Δg, v = 0) fragments arising from the 226 nm photodissociation of jet-cooled O3. Consistent with previously reported trends, the rotational distribution is shifted to higher rotational states with decreasing wavelength. We observe highly suppressed odd rotational state populations due to a strong Λ-doublet propensity. The measured rotational distribution is in agreement with classical trajectory calculations for the v = 0 products, although the distribution is slightly narrower than predicted. The spatial anisotropy follows the previously observed trend of decreasing β with increasing photon energy with β = 0.72 ± 0.14 for v = 0, j = 38. As expected for a triatomic molecule, the v–j correlation is consistent with v perpendicular to j, but the measured correlation is nonlimiting due, in part, to rotational and translational depolarization. The j-dependent line width of the O2(a 1Δg) REMPI spectrum is also discussed in connection with the lifetime of the resonant O2(d 1Πg) state due to predissociation via the II 1Πg valence state.

Despite extensive conceptualization of ions as hard spheres in most textbooks, solid-state structures are more accurately modeled as overlapping soft spheres that better reflect the size of the ions. The corresponding soft-sphere ionic radii of alkali and halide ions can be empirically established from the partial molar volume of the ions in aqueous solution. Partial molar volumes for 15 alkali halide solutes are calculated from the slope of solution density (g/L) versus the solution molarity (mol/L) at the infinite dilution limit. The set of resulting ion sizes for the lithium, sodium, potassium, rubidium, cesium, chloride, bromide, and iodide is both self-consistent, being composed of quantities that are mathematically additive, and physically meaningful. Upon setting the volume of Li­(I) to 5.2 mL/mol, the solid-state structures of all 15 alkali halides, whether rock salt or CsCl, can be constructed to accurately model ion overlap as well as hole volume, though the size ordering of the ions is different than the ordering found for hard spheres. This new conceptual and empirical bridge between the solution and solid phases should help advance the teaching of these commonly disparate subjects by reinforcing aspects of both while drawing new connections between them.