Electronic structure of pyridine-based SAMs on flat Au(111) surfaces: extended charge rearrangements and Fermi level pinning

Density functional theory calculations are used to investigate the electronic structure of pyridine-based self-assembled monolayers (SAMs) on an Au(111) surface. We find that, when using pyridine docking groups, the bonding-induced charge rearrangements are frequently found to extend well onto the molecular backbone. This is in contrast to previous observations for the chemisorption of other SAMs, e.g., organic thiolates on gold, and can be explained by a pinning of the lowest unoccupied states of the SAM at the metal Fermi-level. The details of the pinning process, especially the parts of the molecules most affected by the charge rearrangements, strongly depend on the length of the molecular backbone and the tail-group substituent. We also mention methodological shortcomings of conventional density functional theory that can impact the quantitative details regarding the circumstances under which pinning occurs and highlight a number of peculiarities associated with bond dipoles that arise from Fermi-level pinning.     

Advances in time-differential in-beam Mössbauer spectroscopy

The development of in-beam Mössbauer spectroscopy is described. The potential of the recently applied time-differential technique is discussed. An overview of some recent experimental results is given.     

Über holomorpheP n -Bündel überP 1

Ohne ZusammenfassungDiese Arbeit ist der zweite Teil meiner Dissertation Zur differential-topologischen und analytischen Klassifizierung gewisser algebraischer Mannigfaltigkeiten, als Manuskript vervielfältigt im Math. Inst. der Univ. Bonn. Der erste Teil wurde in [3] veröffentlicht.     

Combinatorial theorems on contractive mappings in power sets

We prove that to every positive integer n there exists a positive integer h such that the following holds: If S is a set of h elements and ƒ a mapping of the power set of S into such that ƒ(T)T for all T , then there exists a strictly increasing sequence T₁T_n of subsets of S such that one of the following three possibilities holds: (a) all sets ƒ(T_i), i= 1,…,n, are equal; (b) for all i=1,…, n, we have ƒ(T_i)=T_i; (c) T_i=ƒ(T_i+1) for all i= 1,…,n-1. This theorem generalizes theorems of the author, Rado, and Leeb. It has applications for subtrees in power sets.     

Effective conjugation and Raman intensities in oligo(para-phenylene)s: a microscopic view from first-principles calculations

Electron-phonon coupling in oligo(para-phenylene)s is addressed in terms of the off-resonance Raman intensities of two distinct modes at 1220 and 1280 cm(-1). On the basis of Albrecht's theory, vibrational coupling and Raman intensities are calculated from first-principles quantum-chemical methods. A few-state model is used to evaluate the dependence of the mode intensities on oligomer length, planarity, and excitation wavelength. The link between electron delocalizationconjugation and Raman intensities is highlighted. Extending on prior studies, the present work focuses on providing an in-depth understanding of the origin of this correlation in addition to reproducing experimental findings. The model applied here allows us to interpret the results on a microscopic, quantum-mechanical basis and to relate the observed trends to the molecular orbital structure and nature of the excited states in this class of materials. We find quantitative agreement between the results of the calculations and those of measurements performed on oligo(para-phenylene)s of various chain lengths in the solid state and in solution.