TDDFT Assessment of Functionals for Optical 0–0 Transitions in Small Radicals

Using LR-TDDFT, we calculated the 0–0 energies of 15 small radicals for which the experimental values in gas phase are available. We used 17 functionals. It turned out that B3LYP, M06-2X, ωB97X-D, CAM-B3LYP, and HSE06 functionals are the most effective functionals in terms of root-mean-square and average unsigned deviation. Using the standard value (0.47 <i>a</i>₀^–1) of the attenuation parameter ω, the long-range-corrected LC-GGA functionals give poor results. However, the LC-PBE with ω = 0.25 <i>a</i>₀^–1 give a performance similar to that of B3LYP. Taking into account zero-point correction improves the results, but the contribution of adiabatic correction is more important than that due to the vibration. The vertical approximation is certainly not recommended. An adiabatic calculation seems to give a good compromise between computing time (and resources) and reliability of the results for most of molecules investigated in this work

Atomistic Mechanisms for the Nucleation of Aluminum Oxide Nanoparticles

A predictive model for nanoparticle nucleation has not yet been successfully achieved. Classical nucleation theory fails because the atomistic nature of the seed has to be considered. Indeed, geometrical structure as well as stoichiometry do not always match the bulk values. We present a fully microscopic approach based on a first-principle study of aluminum oxide clusters. We calculated stable structures of Al_<i>x</i>O_<i>y</i> and their associated thermodynamic properties. From these data, the chemical composition of a gas composed of aluminum and oxygen atoms can be calculated as a function of temperature, pressure, and aluminum to oxygen ratio. We demonstrate the accuracy of this approach in reproducing experimental results obtained with time-resolved spectroscopy of a laser-induced plasma from an Al₂O₃ target. We thus extended the calculation to lower temperatures, i.e., longer time scales, to propose a scenario of composition gas evolution leading to the first alumina seeds

Hydrogen-Induced Adsorption of Carbon Monoxide on the Gold Dimer Cation: A Joint Experimental and DFT Investigation

It is demonstrated, using tandem mass spectrometry and radio frequency ion trap, that the adsorption of a H atom on the gold dimer cation, Au₂H⁺, prevents its dissociation and allows for adsorption of CO. Reaction kinetics are measured by employing a radio frequency ion trap, where Au₂⁺ and CO interact for a given reaction time. The effect of a hydrogen atom is evaluated by comparing reaction rate constants measured for Au₂⁺ and Au₂H⁺. The theoretical results for the adsorption of CO molecules and their reaction characteristics with Au₂⁺ and Au₂H⁺ are found to agree with the experimental findings. The joint investigations provide insights into hydrogen atom adsorption effects and consequent reaction mechanisms