Nuclear quantum effects in calculated NMR shieldings of benzene; a Feynman path integral study

The Feynman path integral Monte Carlo approach has been coupled to the gauge including atomic orbital formalism in order to analyse the absolute magnetic shieldings of the benzene nuclei under the conditions of thermal equilibrium. The Hamiltonian employed in the derivation of ensemble averaged NMR quantities is of the Hartree-Fock type. The basis set used is of 6–31G quality. The spatial delocalization of the atoms leads to a deshielding of both types of benzene nuclei relative to the shieldings experienced at the minimum of the potential energy surface. This deshielding has to be traced back to bond length elongations in thermal equilibrium. The influence of the nuclear fluctuations on the NMR parameters of benzene is quantum driven up to temperatures of 400 K; classical fluctuations are of minor importance in this low-temperature window.     

Selective atomic layer deposition of titanium oxide on patterned self-assembled monolayers formed by microcontact printing

We demonstrate a selective atomic layer deposition of TiO2 thin films on patterned alkylsiloxane self-assembled monolayers. Microcontact printing was done to prepare patterned monolayers of the alkylsiloxane on Si substrates. The patterned monolayers define and direct the selective deposition of the TiO2 thin film using atomic layer deposition. The selective atomic layer deposition is based on the fact that the TiO2 thin film is selectively deposited only on the regions exposing the silanol groups of the Si substrates because the regions covered with the alkylsiloxane monolayers do not have any functional group to react with precursors.