Orientational Phase Transition in the System Pyridine/Ag(111): A Near-Edge X-Ray-Absorption Fine-Structure Study

Bader, Mamoun M.; Haase, J.; Frank, K. H.; Puschmann, A.; Otto, A.

doi:10.1103/physrevlett.56.1921

Cited by 112 publications

(81 citation statements)

References 14 publications

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“…[18d,e, 19a,c] These bands have been assigned to the stretching vibration of NÀAg and NÀAu bonds, respectively. The binding of the pyridine N-end to metal surfaces was also confirmed by the near-edge X-ray absorption fine-structure measurement for pyridine adsorbed on Ag(111), [24] and also by a DFT calculation for pyridine on Au(111). [25] SERS of pyridine adsorbed on the silver-gold bimetallic surfaces were observed in recent studies, and the results indicate that the Raman spectrum of adsorbed pyridine is very sensitive to the surface electronic structure and composition.…”

Section: Introductionmentioning

confidence: 61%

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Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Ren

Zhang

2006

ChemPhysChem

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The binding interactions between pyridine and bimetallic silver-gold clusters are investigated using density functional theory (DFT). The binding energies of pyridine-bimetallic cluster complexes indicate that the bonding depends strongly on the binding site (Au or Ag atom) and bonding molecular orbitals in a given configuration. The donation of the lone-pair electrons of the nitrogen of pyridine to an appropriate unoccupied orbital of each metal cluster plays an important role. The low-lying excited states and charge-transfer states of four stable complexes of interest are calculated on the basis of a time-dependent DFT method. In nonresonance Raman scattering processes, the influence of binding interactions on the relative Raman intensity of totally symmetric pyridine vibrational modes is discussed. These calculated relative Raman intensities are compared with observed surface-enhanced Raman spectra of pyridine adsorbed on silver-gold alloy surfaces.

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Section: Introductionmentioning

confidence: 61%

“…[32] The latter one is expected to be the upper limit of the binding energy of pyridine interacting with silver. For pyridine binding to gold clusters, binding energies of 24 . [54] The binding energy of pyridine/Cu(110) is expected to be close to that of pyridine/gold.…”

Section: Pyàagau 2 and Pyàauagmentioning

confidence: 99%

Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Ren

Zhang

2006

ChemPhysChem

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“…At a higher energy by approximately 4 eV from the LUMO peak, another O* peak is observed both for the two edges and attributed to O* 2 (b 1 ), which corresponds to LUMO+2. 18 Because the energy level of LUMO+1 with a 2 symmetry is lying very closely from the LUMO level, 19 it cannot be clearly distinguished by the present energy resolution.…”

Section: Resultsmentioning

confidence: 91%

“…3. Both for the two edges, a prominent peak is observed at 285.6 eV for C-K and 399.0 eV for N-K, which is associated with excitation to O* 1 (b 1 ) (LUMO), 18,19 and exhibits clear polarization dependence; it is strongly enhanced at the normal incidence. Note that there is a shoulder structure at 285.0 eV for C K-edge.…”

Section: Resultsmentioning

confidence: 96%

Structure and Photo-Induced Charge Transfer of Pyridine Molecules Adsorbed on TiO2(110): A NEXAFS and Core-Hole-Clock Study

et al. 2014

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The structure and photo-induced charge transfer time of pyridine molecules adsorbed on a rutile TiO 2 (110) surface have been studied by near-edge x-ray absorption fine structure (NEXAFS) spectroscopy, density functional theory (DFT) calculations and core-hole-clock (CHC) spectroscopy. Polarization dependence of NEXAFS spectra and geometrical optimization by the DFT calculations revealed that the pyridine molecules are bound to the TiO 2 surface with an upright configuration where the N atom binds to a surface Ti atom. The CHC results indicate that the charge transfer from the LUMO+2 orbital of pyridine with a π* symmetry to the conduction band of TiO 2 is quite fast, where the timescale is less than 3 fs.

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“…Such coverage-dependent molecular reorientations are well known for simpler systems, for example, pyridine adsorbed on Ag(111). [22] In the present case, this Scheme 1. a) Chemical structure of zinc tetra-(3,5-di-tert-butylphenyl)-porphyrin (Zn-TBPP). b) Chemical structure of 4-methoxypyridine, a ligand known to interact with Zn metalloporphyrins through the N atom.…”

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confidence: 84%

A Chemically Switchable Molecular Pinwheel

et al. 2006

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The bottom-up fabrication of nanoscopic devices such as gears, [1] ratchets, [2] turnstiles, [3] switches, [4] and elevators [5] continues to attract much attention. The interest in molecular rotors in solution, [6] inside crystals, [7][8][9] and in the gas phase [10] has recently been extended to surface-mounted rotors; [11][12][13] most recently, a light-driven molecular rotor anchored to a gold surface has been demonstrated, [13] and a recent comprehensive review of artificial molecular rotors is available. [14] Derivatized porphyrins are versatile building blocks for the creation of many different types of assemblies, including supramolecular structures.[15] When adsorbed on surfaces, they can be imaged with scanning tunneling microscopy (STM). Copper tetra-(3,5-di-tert-butylphenyl)porphyrin (Cu-TBPP) adsorbed on Cu(100) was the first case in which singlemolecule manipulation at room temperature [16] and conformational recognition were achieved by means of STM.[17] In subsequent work with Cu-TBPP, Moresco et al. [18] were able to observe tip-induced conformational changes in individual di-tert-butyl phenyl (tBP) groups through height changes in the STM images. More recently, a metal-free TBPP functionalized with cyanophenyl terminal groups and adsorbed on Au(111) was used to form molecular assemblies including tetramers and one-dimensional wires; the structures of these assemblies were controlled by purposeful synthetic design of the monomer molecule.[19] Photoexcited molecular rotors have been observed in solution, [20] and the rotation of individual adsorbed molecules has been induced by manipulation with an STM tip; [11] however, reports of surfacemounted rotors are extremely sparse. [14] We describe herein a self-assembly method for switching on the rotation of adsorbed porphyrin molecules by mounting them on an appropriately functionalized ligand, one end of which binds to the surface, the other to the "hub" of the porphyrin. This was achieved by using zinc tetra-(3,5-di-tert-butylphenyl)porphyrin [21] (Zn-TBPP; Scheme 1 a), whose structure is such that interaction between the macrocycle component and the Ag(100) surface is minimized. As a result of steric repulsion, the four tBP groups at the meso positions of this porphyrin lie essentially orthogonal to the plane of the macrocycle.[17]These tBP "legs" decouple the molecular p-electron system from the silver surface and provide the principal (relatively weak) interaction between the molecule and the metal surface. The result is an adsorbate that is sufficiently strongly bound so as to prevent unwanted diffusion, while at the same time is able to rotate in the plane should the molecule-surface interaction somehow be weakened sufficiently.Zn-TBPP was deposited by evaporation under ultrahigh vacuum (source temperature 573 K) onto an atomically clean single-crystal Ag(100) surface held at 298 K. Individual Zn-TBPP molecules were distributed across the surface by annealing (523 K for 60 mins) and subsequently characterized by STM. Figure 1 shows images obtai...

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Orientational Phase Transition in the System Pyridine/Ag(111): A Near-Edge X-Ray-Absorption Fine-Structure Study

Cited by 112 publications

References 14 publications

Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Structure and Photo-Induced Charge Transfer of Pyridine Molecules Adsorbed on TiO2(110): A NEXAFS and Core-Hole-Clock Study

A Chemically Switchable Molecular Pinwheel

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