Supramolecular organization of chiral molecules on metallic surfaces: <scp>D</scp>‐alaninol on Cu(100) as a case study

Gori, Paola; Contini, G.; Prosperi, T.; Zema, N.; Ronci, F.; Colonna, Stefano; Cricenti, A.; Turchini, S.; Catone, Daniele; Aschi, Massimiliano; Palma, Amedeo

doi:10.1002/pssc.200983821

Cited by 6 publications

(8 citation statements)

References 11 publications

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“…The case of the isolated tetramer of D-alaninol molecules adsorbed on Cu(100) has been analyzed by MD starting from the most stable geometry found for the isolated tetramer through DFT optimization at 0 K. 40 The ED analysis 43 is shown in Figure 7a and reports the eigenvalues of the covariance matrix of all-atom positional fluctuations provided by 50 ns dynamics obtained at RT. The set of ortho-normal eigenvectors produced by covariance matrix diagonalization provides the set of directions along which the system undergoes either conformational transitions, i.e., eigenvectors showing larger eigenvalues, or high-frequency (nearly constrained) oscillations, i.e., small eigenvalues.…”

Section: ' Results and Discussionmentioning

confidence: 99%

“…DFT calculations on an isolated tetrameric structure in gas phase have been validated by MP2 calculations. 40 MD calculations, performed using Gromacs packages, 41 have been carried out, modeling the Cu(100) surface by a three-layer copper slab containing 42 Cu atoms per layer for adsorbed isolated D-alaninol tetramer and 378 Cu atoms per layer for an adsorbed cluster composed of nine tetramers (3 Â 3 matrix); no periodic boundary conditions have been imposed. The interaction between molecules and surface was modeled using the results of DFT calculations for the adsorption of a single Dalaninol molecule on Cu(100) 35,36 where nitrogen is covalently bonded with copper atoms on top.…”

Section: ' Experimental and Computational Methodsmentioning

confidence: 99%

“…A uniform Monkhorst–Pack mesh of 4 × 4 k-points has been used to sample the surface Brillouin zone. DFT calculations on an isolated tetrameric structure in gas phase have been validated by MP2 calculations …”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

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Chirality Transfer from a Single Chiral Molecule to 2D Superstructures in Alaninol on the Cu(100) Surface

et al. 2011

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The formation of 2D chiral monolayers obtained by self-assembly of chiral molecules on surfaces has been widely reported in the literature. Control of chirality transfer from a single molecule to surface superstructures is a challenging and important aspect for tailoring the properties of 2D nanostructures. However, despite the wealth of investigations performed in recent years, how chiral transfer takes place on a large scale still remains an open question. In this paper we report a coupling of scanning tunneling microscopy and low energy electron diffraction measurements with an original theoretical approach, combining molecular dynamics and essential dynamics with density functional theory, to investigate self-assembled chiral structures formed when alaninol adsorbs on Cu(100). The peculiarity of this system is related to the formation of tetrameric molecular structures which constitute the building blocks of the self-assembled chiral monolayer. Such characteristics make alaninol/Cu(100) a good candidate to reveal chiral expression changes. We find that the deposition of alaninol enantiomers results in the formation of isolated tetramers that are aligned along the directions of the substrate at low coverage or when geometrical confinement prevents long-range order. Conversely, a rotation of 14° with respect to the Cu(100) unit vectors is observed when small clusters of tetramers are formed. An insight to the process leading to a 2D globally chiral surface has been obtained by monitoring molecular assemblies as they grow from the early stages of adsorption, suggesting that the distinctive orientation of the self-assembled monolayer originates from a balance of cooperating forces which start acting only when tetramers pack together to form small clusters.

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Section: ' Results and Discussionmentioning

confidence: 99%

Section: ' Experimental and Computational Methodsmentioning

confidence: 99%

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Chirality Transfer from a Single Chiral Molecule to 2D Superstructures in Alaninol on the Cu(100) Surface

et al. 2011

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“…[23][24][25][26][27] Alaninol is a small and conformationally flexible bifunctional chiral amino-alcohol belonging to a group of molecules that are important industrial precursors or intermediates for the synthesis of pharmaceutical compounds. 28 It is known that D-alaninol and L-alaninol adsorbed on Cu (100) surface form an ordered self-assembled chiral saturated monolayer.…”

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confidence: 99%

Transfer of chirality from adsorbed chiral molecules to the substrate highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

et al. 2012

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The study of self-assembled chiral molecules on achiral metallic surfaces is mostly focused on the determination of the geometry of adsorbates and the related electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality transfer from molecules to the substrate by means of circular dichroism in the angular distribution of valence photoelectrons for extended domain of chiral self-assembled molecular structure, formed by alaninol adsorbed on Cu(100). We show that the presence of molecular chiral domains induces chiral electronic states in the interaction with the substrate and locally transfers chiral character to the underneath metal atoms participating in the adsorption process. Identification of chirality in the adsorption footprint represents an important aspect for controlling and tuning the functionality of the molecular-metal interfaces.

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“…In previous works, − Density Functional Theory (DFT) and classical Molecular Dynamics (MD) were employed to interpret experimental evidence in STM, XPS, and LEED spectroscopies; here it has been shown that d -alaninol forms tetrameric clusters at low coverages and an extremely ordered monolayer made of tetrameric units at high coverages. d -Alaninol tetrameric units are aligned along an axis which is rotated by 14° with respect to the [011] direction of the underlying Cu lattice.…”

Section: Introductionmentioning

confidence: 99%

A New Anisotropic Charge-Equilibration Method for Self-Assembly of Organics on Metal Surface: d-Alaninol on Cu(100)

Palma

Satta

2016

J. Chem. Theory Comput.

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The supramolecular chemistry at surfaces has been extensively studied by quantum and classical computational models in order to simulate and reproduce the correct energetics and structures of adsorbed molecules on surfaces at various coverages. We have developed a classical tool able to sample the configuration space overcoming the topological constraints of the standard classical molecular dynamics. Our model is based on the charge equilibration procedure combined with an anisotropic pairwise atomic interaction where an angular dependence, with respect to the metal surface, is explicitly taken into account. The d-alaninol molecule has been chosen as a prototype of a flexible and multifunctional chemical compound which can form manifold complex configurations upon absorption on a metal surface. A detailed analysis of molecular structures and energetics of partial and full coverage has been carried out. The experimental STM image of the monolayer is correctly reproduced by our calculations, indicating that this new approach represents a step forward in the efficient simulation of complex molecular self-assembly.

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Supramolecular organization of chiral molecules on metallic surfaces: D‐alaninol on Cu(100) as a case study

Cited by 6 publications

References 11 publications

Chirality Transfer from a Single Chiral Molecule to 2D Superstructures in Alaninol on the Cu(100) Surface

Chirality Transfer from a Single Chiral Molecule to 2D Superstructures in Alaninol on the Cu(100) Surface

Transfer of chirality from adsorbed chiral molecules to the substrate highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

A New Anisotropic Charge-Equilibration Method for Self-Assembly of Organics on Metal Surface: d-Alaninol on Cu(100)

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