| 1. |
- Fatayer, Shadi, et al.
(författare)
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Reorganization energy upon charging a single molecule on an insulator measured by atomic force microscopy
- 2018
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Ingår i: Nature Nanotechnology. - : Springer Science and Business Media LLC. - 1748-3387 .- 1748-3395. ; 13:5, s. 376-380
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Tidskriftsartikel (refereegranskat)abstract
- Intermolecular single-electron transfer on electrically insulating films is a key process in molecular electronics 1-4 and an important example of a redox reaction 5,6 . Electron-transfer rates in molecular systems depend on a few fundamental parameters, such as interadsorbate distance, temperature and, in particular, the Marcus reorganization energy 7 . This crucial parameter is the energy gain that results from the distortion of the equilibrium nuclear geometry in the molecule and its environment on charging 8,9 . The substrate, especially ionic films 10 , can have an important influence on the reorganization energy 11,12 . Reorganization energies are measured in electrochemistry 13 as well as with optical 14,15 and photoemission spectroscopies 16,17 , but not at the single-molecule limit and nor on insulating surfaces. Atomic force microscopy (AFM), with single-charge sensitivity 18-22 , atomic-scale spatial resolution 20 and operable on insulating films, overcomes these challenges. Here, we investigate redox reactions of single naphthalocyanine (NPc) molecules on multilayered NaCl films. Employing the atomic force microscope as an ultralow current meter allows us to measure the differential conductance related to transitions between two charge states in both directions. Thereby, the reorganization energy of NPc on NaCl is determined as (0.8 ± 0.2) eV, and density functional theory (DFT) calculations provide the atomistic picture of the nuclear relaxations on charging. Our approach presents a route to perform tunnelling spectroscopy of single adsorbates on insulating substrates and provides insight into single-electron intermolecular transport.
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| 2. |
- Nowakowska, Sylwia, et al.
(författare)
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Adsorbate-Induced Modification of the Confining Barriers in a Quantum Box Array
- 2018
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 12:1, s. 768-778
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Tidskriftsartikel (refereegranskat)abstract
- Quantum devices depend on addressable elements, which can be modified separately and in their mutual interaction. Self-assembly at surfaces, for example, formation of a porous (metal-) organic network, provides an ideal way to manufacture arrays of identical quantum boxes, arising in this case from the confinement of the electronic (Shockley) surface state within the pores. We show that the electronic quantum box state as well as the interbox coupling can be modified locally to a varying extent by a selective choice of adsorbates, here C60, interacting with the barrier. In view of the wealth of differently acting adsorbates, this approach allows for engineering quantum states in on-surface network architectures.
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| 3. |
- Nowakowska, Sylwia, et al.
(författare)
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Configuring Electronic States in an Atomically Precise Array of Quantum Boxes
- 2016
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Ingår i: Small. - : Wiley-VCH Verlagsgesellschaft. - 1613-6810 .- 1613-6829. ; 12:28, s. 3757-3763
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Tidskriftsartikel (refereegranskat)abstract
- A 2D array of electronically coupled quantum boxes is fabricated by means of on-surface self-assembly assuring ultimate precision of each box. The quantum states embedded in the boxes are configured by adsorbates, whose occupancy is controlled with atomic precision. The electronic interbox coupling can be maintained or significantly reduced by proper arrangement of empty and filled boxes.
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| 4. |
- Nowakowska, Sylwia, et al.
(författare)
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Interplay of weak interactions in the atom-by-atom condensation of xenon within quantum boxes
- 2015
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 21:6, s. 6071-
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Tidskriftsartikel (refereegranskat)abstract
- Condensation processes are of key importance in nature and play a fundamental role in chemistry and physics. Owing to size effects at the nanoscale, it is conceptually desired to experimentally probe the dependence of condensate structure on the number of constituents one by one. Here we present an approach to study a condensation process atom-by-atom with the scanning tunnelling microscope, which provides a direct real-space access with atomic precision to the aggregates formed in atomically defined 'quantum boxes'. Our analysis reveals the subtle interplay of competing directional and nondirectional interactions in the emergence of structure and provides unprecedented input for the structural comparison with quantum mechanical models. This approach focuses on-but is not limited to-the model case of xenon condensation and goes significantly beyond the well-established statistical size analysis of clusters in atomic or molecular beams by mass spectrometry.
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| 5. |
- Shchyrba, Aneliia, et al.
(författare)
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Controlling the dimensionality of on-surface coordination polymers via endo- or exoligation
- 2014
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 136:26, s. 9355-9363
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Tidskriftsartikel (refereegranskat)abstract
- The formation of on-surface coordination polymers is controlled by the interplay of chemical reactivity and structure of the building blocks, as well as by the orientating role of the substrate registry. Beyond the predetermined patterns of structural assembly, the chemical reactivity of the reactants involved may provide alternative pathways in their aggregation. Organic molecules, which are transformed in a surface reaction, may be subsequently trapped via coordination of homo- or heterometal adatoms, which may also play a role in the molecular transformation. The amino-functionalized perylene derivative, 4,9-diaminoperylene quinone-3,10-diimine (DPDI), undergoes specific levels of dehydrogenation (-1 H-2 or -3 H-2) depending on the nature of the present adatoms (Fe, Co, Ni or Cu). In this way, the molecule is converted to an endo- or an exoligand, possessing a concave or convex arrangement of ligating atoms, which is decisive for the formation of either ID or 2D coordination polymers.
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