A model of melamine molecules ordering on metal surfaces.

The model of melamine molecules ordering into planar honeycomb and closed packed phases is proposed. To account for the "side-to-side" melamine-melamine molecular interactions, we use the version of the antiferromagnetic Blume-Capel model with some exclusions. The model is solved by Monte Carlo calculations on a triangular lattice, a slightly rescaled version of Au(111) and Ag(111) lattices on which the main experimental data are obtained. The ordered phases are formed when mutual distance between the centers of molecules is within sixth and seventh nearest neighbor distances of rescaled substrate lattice. We obtain the ground state phase diagram with honeycomb and three closed-packed phases and density-temperature phase diagram with three pure phases (gas, honeycomb, and close-packed) and their two-phase coexistences.

Pin-wheel hexagons: a model for anthraquinone ordering on Cu(111).

The 4-state model of anthraquinone molecules ordering in a pin-wheel large-pore honeycomb phase on Cu(111) is proposed and solved by Monte Carlo simulation. The model is defined on a rescaled triangular lattice with the lattice constant a being equal to intermolecular distance in the honeycomb phase. The pin-wheel triangle formations are obtained taking into account the elongated shape of the molecules and anisotropic interactions for main two attractive short range (double and single dimeric) H-bond interactions. The long-range intermolecular interactions, corresponding to repulsive dipole-dipole forces, are assumed to be isotropic. Also, a very small (compared to short-range forces) isotropic attractive long-range interaction at the "characteristic" distance of a pore diameter is employed, and its effect carefully studied. This interaction is crucial for a formation of closed porous ordered systems, pin-wheel hexagons in particular. If each side of a pin-wheel hexagon is formed of n parallel molecules, the distance of this characteristic interaction is a√(3n(2)+1). The phase diagrams including different pin-wheel hexagon phases and a variety of other ordered structures are obtained. By changing the distance of characteristic interaction, different ordering routes into the experimental pin-wheel honeycomb phase are explored. The results obtained imply that classical explanation of the origin of the pin-wheel honeycomb phase in terms of some balance of attractive and repulsive forces cannot be totally discounted yet.

Magnetic excitation and readout of methyl group tunnel coherence.

Methyl groups are ubiquitous in synthetic materials and biomolecules. At sufficiently low temperature, they behave as quantum rotors and populate only the rotational ground state. In a symmetric potential, the three localized substates are degenerate and become mixed by the tunnel overlap to delocalized states separated by the tunnel splitting ν t . Although ν t can be inferred by several techniques, coherent superposition of the tunnel-split states and direct measurement of ν t have proven elusive. Here, we show that a nearby electron spin provides a handle on the tunnel transition, allowing for its excitation and readout. Unlike existing dynamical nuclear polarization techniques, our experiment transfers polarization from the electron spin to methyl proton spins with an efficiency that is independent of the magnetic field and does not rely on an unusually large tunnel splitting. Our results also demonstrate control of quantum states despite the lack of an associated transition dipole moment.

Isostructural phase transition, quasielastic neutron scattering and magnetic resonance studies of a bistable dielectric ion-pair crystal [(CH3)2NH2]2KCr(CN)6.

We have synthesised and characterised a novel organic-inorganic hybrid crystal, [(CH3)2NH2]2KCr(CN)6. The thermal DSC, TMA, DTG and DTA analyses indicate two solid-to-solid structural phase transitions (PTs). According to the X-ray diffraction experiments, the first PT at 220 K is isostructural, since it does not involve a change of the space group. This transition occurs between the states, where the (CH3)2NH2+ cations are orientationally disordered and ordered (frozen). The other reversible PT at 481 K leads to a melt-like phase similar to the one observed in plastic crystals or polar liquids. Dielectric spectroscopy has been used to characterise the switching properties of the dipole moments in the vicinity of the PTs. Continuous-wave electron paramagnetic resonance spectroscopy was employed to investigate the effect of ordering on the local environment of the Cr3+ ions. We have also applied the quasielastic neutron scattering (QENS) technique as well as 1H NMR spectroscopy to measure the dynamics of the (CH3)2NH2+ cations residing in the inorganic framework.

Self-assembly of 5,6-dihydroxyindole-2-carboxylic acid: polymorphism of a eumelanin building block on Au(111).

Investigating two-dimensional (2D) self-assembled structures of biological monomers governed by intermolecular interactions is a prerequisite to understand the self-assembly of more complex biomolecular systems. 5,6-Dihydroxyindole carboxylic acid (DHICA) is one of the building blocks of eumelanin - an irregular heteropolymer and the most common form of melanin which has potential applications in organic electronics and bioelectronics. By means of scanning tunneling microscopy, density functional theory and Monte Carlo calculations, we investigate DHICA molecular configurations and interactions underlying the multiple 2D patterns formed on Au(111). While DHICA self-assembled molecular networks (SAMNs) are dominated by the hydrogen bonding of carboxylic acid dimers, a variety of 2D architectures are formed due to the multiple weak interactions of the catechol group. The hydroxyl group also allows for redox reactions, caused by oxidation via O2 exposure, resulting in molecular rearrangement. The susceptibility of the molecules to oxidation is affected by their SAMNs architectures, giving insights on the reactivity of indoles as well as highlighting non-covalent assembly as an approach to guide selective oxidation reactions.

Temperature-induced molecular reorganization on Au(111) driven by oligomeric defects.

The formation of ordered molecular structures on surfaces is determined by the balance between molecule-molecule and molecule-substrate interactions. Whether the aggregation process is guided by non-covalent forces or on-surface reactions, a deeper understanding of these interactions is pivotal to formulating a priori predictions of the final structural features and the development of bottom-up fabrication protocols. Theoretical models of molecular systems corroborate the information gathered through experimental observations and help explain the thermodynamic factors that underpin on-surface phase transitions. Here, we report a scanning tunneling microscopy investigation of a tribromo-substituted heterotriangulene on the Au(111) surface, which initially forms an extended close-packed ordered structure stabilized by BrBr halogen bonds when deposited at room temperature. X-ray photoelectron spectroscopy reveals that annealing the self-assembled layer induces a fraction of the molecular precursors to partially dehalogenate that in turn leads to the formation of a less stable BrO non-covalent network which coexists with the short oligomers. Density functional theory (DFT) and Monte Carlo (MC) simulations illustrate how dimer moieties act as defects whose steric hindrance prevents the retention of the more stable configuration. A small number of dimers is sufficient to drive the molecular reorganization into a lower cohesive energy phase. Our study shows the importance of a combined DFT - MC approach to understand the evolution of molecular systems on substrates.

Reorientational dynamics of organic cations in perovskite-like coordination polymers.

Here we report the dynamics of organic cations as guest molecules in a perovskite host-framework. The molecular motion of CH3NH3+ (MAFe), (CH3)2NH2+ (DMAFe) and (CH3)3NH+ (TrMAFe) in the cage formed by KFe(CN)63- units was studied using a combination of experimental methods: (i) thermal analysis, (ii) dielectric and electric studies, (iii) optical observations, (iv) EPR and 1H NMR spectroscopy and (v) quasielastic neutron scattering (QENS). In the case of MAFe and TrMAFe, the thermal analysis reveals one solid-to-solid phase transition (PT) and two PTs for the DMAFe crystal. A markedly temperature-dependent dielectric constant indicates the tunable and switchable properties of the complexes. Also, their semiconducting properties are confirmed by a dc conductivity measurement. The broadband dielectric relaxation is analyzed for the TrMAFe sample in the frequency range of 100 Hz-1 GHz. QENS shows that we deal rather with the localized motion of the cation than a diffusive one. Three models, which concern the simultaneous rotation of the CH3 and/or NH3 group, π-flips and free rotations of the organic cation, are used to fit the elastic incoherent structure factor. The 1H NMR spin-lattice relaxation time for all compounds under study, as well as the second moments, has been measured in a wide temperature range. In all studied samples, the temperature dependence of the second moment of the proton NMR line indicated the gradual evolution of the molecular movements from the rigid state up to a highly disordered one.

Room-temperature surface-assisted reactivity of a melanin precursor: silver metal-organic coordination versus covalent dimerization on gold.

The ability of catecholamines to undergo oxidative self-polymerization provides an attractive route for preparation of coatings for biotechnology and biomedicine applications. However, efforts toward developing a complete understanding of the mechanism that underpins polymerization have been hindered by the multiple catechol crosslinking reaction pathways that occur during the reaction. Scanning tunneling microscopy allows the investigation of small molecules in a reduced-complexity environment, providing important insight into how the intermolecular forces drive the formation of supramolecular assemblies in a controlled setting. Capitalizing on this approach, we studied the self-assembly of 5,6-dihydroxy-indole (DHI) on Au(111) and Ag(111) to investigate the interactions that affect the two-dimensional growth mechanism and to elucidate the behavior of the catechol group on these two surfaces. X-ray photoelectron spectroscopy, together with density functional theory and Monte Carlo modeling, helps unravel the differences between the two systems. The molecules form large ordered domains, yet with completely different architectures. Our data reveal that some of the DHI molecules deposited on Ag are in a modified redox state, with their catechol group oxidized into quinone. On Ag(111), the molecules are deposited in long-range lamellar patterns stabilized by metal-organic coordination, while covalent dimer pairs are observed on Au(111). We also show that the oxidation susceptibility is affected by the substrate, with the DHI/Au remaining inert even after being exposed to O2 gas.

Antiferromagnetic triangular Blume-Capel model with hard-core exclusions.

Using Monte Carlo simulation, we analyze phase transitions of two antiferromagnetic (AFM) triangular Blume-Capel (BC) models with AFM interactions between third-nearest neighbors. One model has hard-core exclusions between the nearest-neighbor (1NN) particles (3NN1 model) and the other has them between the nearest-neighbor and next-nearest-neighbor particles (3NN12 model). Finite-size scaling analysis reveals that in these models, the transition from the paramagnetic to long-range order (LRO) AFM phase is either of the first order or goes through an intermediate phase which might be attributed to the Berezinskii-Kosterlitz-Thouless (BKT) type. The properties of the low-temperature phase transition to the AFM phase of the 1NN, 3NN1, and 3NN12 models are found to be very similar for almost all values of a normalized single-ion anisotropy parameter, 0 < δ < 1.5. Higher temperature behavior of the 3NN12 and 3NN1 models is rather different from that of the 1NN model. Three phase transitions are observed for the 3NN12 model: from the paramagnetic phase to the phase with domains of the LRO AFM phase at T(c), from this structure to the diluted frustrated BKT-type phase at T(2), and from the frustrated phase to the AFM LRO phase at T(1). For the 3NN12 model, T(c) > T(2) > T(1) at 0 < δ < 1.15 (range I), T(c) ≈ T(2) > T(1) at 1.15 < δ < 1.3 (range II), and T(c) = T(2) = T(1) at 1.3 < δ < 1.5 (range III). For the 3NN1 model, T(c) ≈ T(2) > T(1) at 0 < δ < 1.2 (range II) and T(c) = T(2) = T(1) at 1.2 < δ < 1.5 (range III). There is only one first-order phase transition in range III. The transition at T(c) is of the first order in range II and either of a weak first order or a second order in range I.

Phase transition properties of the Bell-Lavis model.

Using Monte Carlo calculations we analyze the order and the universality class of phase transitions into a low-density (honeycomb) phase of a triangular antiferromagnetic three-state Bell-Lavis model. The results are obtained in a whole interval of chemical potential µ corresponding to the honeycomb phase. Our results demonstrate that the phase transitions might be attributed to the three-state Potts universality class for all µ values except for the edges of the honeycomb phase existence. At the honeycomb phase and the low-density gas phase boundary the transitions become of the first order. At another, honeycomb-to-frustrated phase boundary, we observe the approach to the crossover from the three-state Potts to the Ising model universality class. We also obtain the Schottky anomaly in the specific heat close to this edge. We show that the intermediate planar phase, found in a very similar antiferromagnetic triangular Blume-Capel model, does not occur in the Bell-Lavis model.