Nonalternant aromatic π-electron systems show promises for surface functionalization due to their unusual electronic structure. Based on our previous experiences for metal surfaces, we investigate the adsorption structures, adsorption dynamics and bonding characteristics of azulene and its alternant aromatic isomer naphthalene on the Si(001) surface. Using a combination of density functional theory, ab initio molecular dynamics, reaction path sampling and bonding analysis with the energy decomposition analysis for extended systems, we show that azulene shows direct adsorption paths into several, strongly bonded chemisorbed final structures with up to four covalent carbon–silicon bonds which can be described in a donor–acceptor and a shared-electron bonding picture nearly equivalently. Naphthalene also shows these tetra-σ-type bonding structures in accordance with an earlier study. But the adsorption path is pseudo-direct here with a precursor intermediate bonded via one aromatic ring and strong indications for a narrow adsorption funnel. The four surface-adsorbate bonds formed lead for both adsorbates to a strong corrugation and a loss of aromaticity.

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The surfaces of waimirite β-YF 3 have been studied for their fluorine and chlorine versus water affinity. Bonding patterns of HF, HCl, and H 2 O chemically adsorbed onto surfaces of ( 010), ( 100), (011), and (101) have been quantified by density functional theory applying energy decomposition analysis. We found that the adsorption of H 2 O is dominated by about 65% of electrostatics, which causes a low surface sensitivity and weak interactions. On the contrary, the adsorptions of HF and HCl are driven by strong hydrogen bonds resulting in a highly surface-dependent ratio of 30-60% electrostatic versus orbital contribution. Among the stoichiometric surfaces, the shortest and strongest hydrogen bonds and consequently most covalent bonding patterns are found within YF 3 ÁHCl. However, when including the preparation energy, each surface favors the adsorption of HF over HCl, which reproduces the higher affinity of yttrium towards fluoride over chloride, previously known for solutions, also for the solid state.

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