Self-assembled monolayers of polar molecules on Au(111) surfaces: distributing the dipoles
文献信息
David A. Egger, Ferdinand Rissner, Gerold M. Rangger, Oliver T. Hofmann, Lukas Wittwer, Georg Heimel, Egbert Zojer
Quantum-mechanical calculations are performed to investigate the interface between Au(111) surfaces and self-assembled monolayers (SAMs) of organic thiols. Dipolar pyrimidine units act as building blocks to systematically tune the molecular dipole moments via the number of repeat units. The resulting work-function modifications and the energetic alignment of the frontier electronic states in the SAM with the Fermi level are analyzed. Compared to SAMs where strong dipole moments are realized only by end-group substitutions on otherwise non-polar molecules, an entirely different evolution with backbone length is found for the present systems, where dipoles are built directly into the backbone. In particular, the achievable work-function modifications depend on peculiarities in the relative alignment of the energy levels in the SAM and in the metal. We thus introduce an additional degree of freedom for tuning surface and interface electronic properties with functional self-assembled monolayers.
期刊推荐

Physical Chemistry Chemical Physics

Nature Reviews Drug Discovery

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Angewandte Chemie International Edition

Molecular Diversity

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European Journal of Organic Chemistry

Journal of Enzyme inhibition and Medicinal Chemistry

Mini-Reviews in Medicinal Chemistry

Foundations of Chemistry
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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