Steric and chain length effects in the (√(3)×√(3))R30° structures of alkanethiol self-assembled monolayers on Au(111).

The translational and orientational potential energy surfaces (PESs) of n-alkanethiols with up to four carbon atoms are studied for (√(3)×√(3))R30° self-assembled monolayers (SAMs). The PESs indicate that methanethiol may form SAM structures that are not accessible for long-chain thiols. The tilt of the thiol molecules is determined by a compromise between the preferred binding geometry at the sulfur atom and the steric requirements of the alkane chains. The Au-S bond lengths, offset from the bridge position (brg), and the Au-S-C bond angles result in tilt angles of the S-C bond in the range of 55-60°. As DFT/generalized gradient approximation systematically underestimates chain-chain interactions, the binding energies are corrected by comparison to MP2 interaction energies of alkane dimers in SAM-like configurations. The resulting thiol binding energies increase by approximately 1 kcal mol(-1) per CH(2) group, which results in a substantial stabilization of long-chain SAMs due to chain-chain interactions. Furthermore, as the chain length increases, the accessible range of backbone tilt angles is constrained due to steric effects. The combination of these two effects may explain why SAM structures with long-chain thiols exhibit higher order in experiments. For each thiol two favorable SAM structures are found with the sulfur head group at the fcc-brg and hcp-brg positions, respectively. These domains may coexist in thermal equilibrium. In combination with the symmetry of the gold (111) surface, this raises the possibility of up to six different domains on single-crystal terraces. Reconstructions by an adatom or vacancy of ethanethiol SAMs with (√(3)×√(3))R30° lattice are also studied using PES scans. The results indicate that adsorption of thiols next to a vacancy is favorable and may lead to point defects inside SAMs.

Computational studies on polymer adhesion at the surface of gamma-Al2O3. I. The adsorption of adhesive component molecules from the gas phase.

We calculate the minimum energy paths and reaction energies of the adsorption of the epoxide adhesive components diglycidylesterbisphenol A (DGEBA), diethyltriamine (DETA), and the adhesion promoter 3-aminopropylmethoxysilane (AMEO) at two different sites on a model of the native Al2O3 surface, using the nudged elastic band algorithm in conjunction with self-consistent charge-density functional based tight binding. Our results show that the chosen combination of methods is well suited to obtain an overview of the reaction mechanisms and kinetics of the adsorption of organic molecules on inorganic surfaces. The obtained MEP-s show that there is preference for the adsorption of the adhesion promoter, AMEO, over the resin, DGEBA, while the adsorption of the curing agent, DETA, is unfavorable. Our approach also gives an insight into the ranges of the mechanical and electronic influences of the adsorption process on the interface, which neither full ab initio methods nor force field approaches can provide. These results will help to develop a quantum mechanics-molecular mechanics multiscale embedding scheme for more detailed studies of organic/inorganic hybrid interface reactions.