Triphenylene-Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge-Transfer Complexes with Common Unoccupied Molecular States.

Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule-substrate interactions. Here, the formation of a monolayer thick blend of triphenylene-based organic donor and acceptor molecules from 2,3,6,7,10,11-hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low-energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self-assembled charge-transfer complexes.

Patients' Self-presentational Tactics as Predictors of the Early Therapeutic Alliance.

OBJECTIVES: The early therapeutic alliance is an important predictor for therapy outcome. However, knowledge about predictors of the therapeutic alliance is still limited. We examined if patients' self-presentational behaviors can predict the early therapeutic alliance. METHOD: Videotaped intake interviews of 60 randomly selected patients were coded for patients' self-presentational tactics. The therapeutic alliance was measured with the Bern Post-Session Report. RESULTS: From the therapists' perspective, Agenda setting and Self-promotion were positively related and Supplication was negatively related to the therapeutic alliance. From the patients' perspective, Agenda setting was negatively related and Self-promotion was positively related to the therapeutic alliance. Provoking a response from the therapist was unrelated to the therapeutic alliance as judged from both therapist and patient perspectives. Correlations were of small-to-moderate size. These findings have important implications for building a constructive therapeutic alliance and identifying patients' needs. CONCLUSIONS: Patients' self-presentational behavior is a promising predictor of the early therapeutic alliance.

On-surface synthesis of π-conjugated ladder-type polymers comprising nonbenzenoid moieties.

On-surface synthesis provides a powerful approach toward the atomically precise fabrication of π-conjugated ladder polymers (CLPs). We report herein the surface-assisted synthesis of nonbenzenoid CLPs from cyclopenta-annulated anthracene monomers on Au(111) under ultrahigh vacuum conditions. Successive thermal annealing steps reveal the dehalogenative homocoupling to yield an intermediate 1D polymer and the subsequent cyclodehydrogenation to form the fully conjugated ladder polymer. Notably, neighbouring monomers may fuse in two different ways, resulting in six- and five-membered rings, respectively. The structure and electronic properties of the reaction products have been investigated via low-temperature scanning tunneling microscopy and spectroscopy, complemented by density-functional theory calculations. Our results provide perspectives for the on-surface synthesis of nonbenzenoid CLPs with the potential to be used for organic electronic devices.

A framework for definition of logical scenarios for safety assurance of automated driving.

Objective: In order to introduce automated vehicles on public roads, it is necessary to ensure that these vehicles are safe to operate in traffic. One challenge is to prove that all physically possible variations of situations can be handled safely within the operational design domain of the vehicle. A promising approach to handling the set of possible situations is to identify a manageable number of logical scenarios, which provide an abstraction for object properties and behavior within the situations. These can then be transferred into concrete scenarios defining all parameters necessary to reproduce the situation in different test environments. Methods: This article proposes a framework for defining safety-relevant scenarios based on the potential collision between the subject vehicle and a challenging object, which forces the subject vehicle to depart from its planned course of action to avoid a collision. This allows defining only safety-relevant scenarios, which can directly be related to accident classification. The first criterion for defining a scenario is the area of the subject vehicle with which the object would collide. As a second criterion, 8 different positions around the subject vehicle are considered. To account for other relevant objects in the scenario, factors that influence the challenge for the subject vehicle can be added to the scenario. These are grouped as action constraints, dynamic occlusions, and causal chains. Results: By applying the proposed systematics, a catalog of base scenarios for a vehicle traveling on controlled-access highways has been generated, which can directly be linked to parameters in accident classification. The catalog serves as a basis for scenario classification within the PEGASUS project. Conclusions: Defining a limited number of safety-relevant scenarios helps to realize a systematic safety assurance process for automated vehicles. Scenarios are defined based on the point of the potential collision of a challenging object with the subject vehicle and its initial position. This approach allows defining scenarios for different environments and different driving states of the subject vehicle using the same mechanisms. A next step is the generation of logical scenarios for other driving states of the subject vehicle and for other traffic environments.