| 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. |
- Larsson, Andreas, et al.
(författare)
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Orientation of individual C60 molecules adsorbed on Cu(111) : Low-temperature scanning tunneling microscopy and density functional calculations
- 2008
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 77:11
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Tidskriftsartikel (refereegranskat)abstract
- Density functional theory (DFT) and low-temperature scanning tunneling microscopy (STM) have been combined to examine the bonding of individual C60 molecules on Cu(111). Energy-resolved differential-conductance maps have been measured for individual C60 molecules adsorbed on a Cu(111) surface by means of low-temperature STM, which are compared to and complemented by theoretically computed spectral images. It has been found that C60 chemisorbs with a six-membered ring parallel to the surface at two different Cu(111) binding sites that constitute two exclusive hexagonal sublattices. On each sublattice, C60 is bonded in one particular rotational conformer, i.e., C60 molecules bind to the Cu(111) surface in two different azimuthal orientations differing by 60°depending on which sublattice the binding site belongs to. The binding conformation of C60 and its orientation with regard to the copper surface can be deduced by this joint experimental-theoretical approach. Six possible pairs of C60 configurations on three different Cu surface binding sites have been identified that fulfil the requirements of the two sublattices and are consistent with all experimental and theoretical data. Theory proposes that two of these configuration pairs are most likely. We have found that DFT does not get the binding energy between rotational conformers in the correct order. We also report two different C60 monolayers on Cu(111): one with alternating orientations of neighboring molecules at low temperature and the other with (4×4) structure after annealing above room temperature.
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| 3. |
- Mohn, Fabian, et al.
(författare)
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Reversible Bond Formation in a Gold-Atom-Organic-Molecule Complex as a Molecular Switch
- 2010
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Ingår i: Physical Review Letters. - 1079-7114 .- 0031-9007. ; 105:26
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Tidskriftsartikel (refereegranskat)abstract
- We report on the formation of a metal-molecule complex that can be used as a molecular switch. Using a cryogenic scanning tunneling microscope, a covalent bond was formed reversibly between a gold atom and a perylene-3,4,9,10-tetracarboxylic dianhydride molecule supported by a thin insulating film. The bonded and the nonbonded state of the complex were found to be associated with different charge states, and the switching between the two states was accompanied by a considerable change in the tunneling current. Atomic force microscopy molecular imaging was employed to determine precisely the atomic structure of the complex, and the experimental results were corroborated by density functional theory calculations.
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| 4. |
- Olsson, Eva, 1960, et al.
(författare)
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Multiple Charge States of Ag Atoms on Ultrathin NaCl Films
- 2007
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Ingår i: Phys. Rev. Lett.. ; 98, s. 176803-
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Tidskriftsartikel (refereegranskat)abstract
- A combined study using density functional calculations and scanning tunneling microscopy experiments shows that individual silver adatoms on ultrathin sodium chloride films on copper surfaces are stable in three different charge states—neutral, negatively, and positively charged adatoms. The charge states of the individual adatoms were manipulated by voltage pulses. The key parameters determining the stability of various charge states are identified and discussed within a simple model.
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| 5. |
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| 6. |
- Repp, Jascha, et al.
(författare)
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Controlling the Charge State of Individual Gold Adatoms
- 2004
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 305, s. 493-
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Tidskriftsartikel (refereegranskat)abstract
- The nature and control of individual metal atoms on insulators are of great importance in emerging atomic-scale technologies. Individual gold atoms on an ultrathin insulating sodium chloride film supported by a copper surface exhibit two different charge states, which are stabilized by the large ionic polarizability of the film. The charge state and associated physical and chemical properties such as diffusion can be controlled by adding or removing a single electron to or from the adatom with a scanning tunneling microscope tip. The simple physical mechanism behind the charge bistability in this case suggests that this is a common phenomenon for adsorbates on polar insulating films.
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| 7. |
- Repp, Jascha, et al.
(författare)
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Imaging Bond Formation Between a Gold Atom and Pentacene on an Insulating Surface
- 2006
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 312:5777, s. 1196-1199
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Tidskriftsartikel (refereegranskat)abstract
- A covalent bond between an individual pentacene molecule and a gold atom was formed by means of single-molecule chemistry inside a scanning tunneling microscope junction. The bond formation is reversible, and different structural isomers can be produced. The single-molecule synthesis was done on ultrathin insulating films that electronically isolated the reactants and products from their environment. Direct imaging of the orbital hybridization upon bond formation provides insight into the energetic shifts and occupation of the molecular resonances.
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| 9. |
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