On the energetics of conformational switching of molecules at and close to room temperature.

We observe and induce conformational switching of individual molecules via scanning tunneling microscopy (STM) at and close to room temperature. 2H-5,10,15,20-Tetrakis-(3,5-di-tert-butyl)-phenylporphyrin adsorbed on Cu(111) forms a peculiar supramolecular ordered phase in which the molecules arrange in alternating rows, with two distinct appearances in STM which are assigned to concave and convex intramolecular conformations. Around room temperature, frequent bidirectional conformational switching of individual molecules from concave to convex and vice versa is observed. From the temperature dependence, detailed insights into the energy barriers and entropic contributions of the switching processes are deduced. At 200 K, controlled STM tip-induced unidirectional switching is possible, yielding an information storage density of 4.9 × 10(13) bit/inch(2). With this contribution we demonstrate that controlled switching of individual molecules at comparably high temperatures is possible and that entropic effects can be a decisive factor in potential molecular devices at these temperatures.

Kinetics of the sulfur oxidation on palladium: a combined in situ x-ray photoelectron spectroscopy and density-functional study.

We studied the reaction kinetics of sulfur oxidation on the Pd(100) surface by in situ high resolution x-ray photoelectron spectroscopy and ab initio density functional calculations. Isothermal oxidation experiments were performed between 400 and 500 K for small amounts (~0.02 ML) of preadsorbed sulfur, with oxygen in large excess. The main stable reaction intermediate found on the surface is SO(4), with SO(2) and SO(3) being only present in minor amounts. Density-functional calculations depict a reaction energy profile, which explains the sequential formation of SO(2), SO(3), and eventually SO(4), also highlighting that the in-plane formation of SO from S and O adatoms is the rate limiting step. From the experiments we determined the activation energy of the rate limiting step to be 85 ± 6 kJ mol(-1) by Arrhenius analysis, matching the calculated endothermicity of the SO formation.

Adsorption and reaction of SO2 on clean and oxygen precovered Pd(100)--a combined HR-XPS and DF study.

We studied the adsorption and reactivity of SO(2) on clean and oxygen precovered Pd(100) with high resolution X-ray photoelectron spectroscopy and density functional calculations. Upon adsorption at 120 K two different SO(2) species were detected, which were identified as upright-standing and flat-lying molecules by comparing the calculated core level shifts. In agreement with the relative stabilities determined by the calculations the intensities of the photoelectron spectra indicate that the majority species are upright-standing SO(2). Upon heating the quantitative analysis of the data indicates desorption of SO(3) and formation of atomic sulfur. On the oxygen precovered surface small amounts of SO(3) are formed already upon SO(2) adsorption at low temperatures. Upon heating stepwise oxidation of SO(2) to SO(3) and, eventually, to SO(4) is found. Two different SO(4) species were detected, which are assigned to SO(4) bound in the proximity of or remote from oxygen adatoms, according to core level shift estimates.