Luca Muccioli

Surface Supramolecular Organization of a Terbium(III) Double-Decker Complex on Graphite and its Single Molecule Magnet Behavior

The two-dimensional self-assembly of a terbium(III) double-decker phthalocyanine on highly oriented pyrolitic graphite (HOPG) was studied by atomic force microscopy (AFM), and it was shown that it forms highly regular rectangular two-dimensional nanocrystals on the surface, that are aligned with the graphite symmetry axes, in which the molecules are organized in a rectangular lattice as shown by scanning tunneling microscopy. Molecular dynamics simulations were run in order to model the behavior of a collection of the double-decker complexes on HOPG. The results were in excellent agreement with the experiment, showing that-after diffusion on the graphite surface-the molecules self-assemble into nanoscopic islands which align preferentially along the three main graphite axes. These low dimension assemblies of independent magnetic centers are only one molecule thick (as shown by AFM) and are therefore very interesting nanoscopic magnetic objects, in which all of the molecules are in interaction with the graphite substrate and might therefore be affected by it. The magnetic properties of these self-assembled bar-shaped islands on HOPG were studied by X-ray magnetic circular dichroism, confirming that the compounds maintain their properties as single-molecule magnets when they are in close interaction with the graphite surface.

Towards in silico liquid crystals. Realistic transition temperatures and physical properties for n-cyanobiphenyls via molecular dynamics simulations.

We study the important n-cyanobiphenyl (with n= 4-8) series of mesogens, using modelling and molecular dynamics simulations. We are able to obtain spontaneously ordered nematics upon cooling isotropic samples of 250 molecules. By using the united-atom force field developed herein, we show that the experimental isotropic-nematic transition temperatures are reproduced within 4 K, allowing a molecular-level interpretation of the odd-even effect along the series. Other properties, like densities, orientational order parameters and NMR residual dipolar couplings are also reproduced well, demonstrating the feasibility of predictive in silico modelling of nematics from the molecular structure.

How does the trans{cis photoisomerization of azobenzene take place in organic solvents?

The trans-cis photoisomerization of azobenzene-containing materials is key to a number of photomechanical applications, but the actual conversion mechanism in condensed phases is still largely unknown. Herein, we study the n, pi* isomerization in a vacuum and in various solvents via a modified molecular dynamics simulation adopting an ab initio torsion-inversion force field in the ground and excited states, while allowing for electronic transitions and a stochastic decay to the fundamental state. We determine the trans-cis photoisomerization quantum yield and decay times in various solvents (n-hexane, anisole, toluene, ethanol, and ethylene glycol), and obtain results comparable with experimental ones where available. A profound difference between the isomerization mechanism in vacuum and in solution is found, with the often neglected mixed torsional-inversion pathway being the most important in solvents.

Computer simulations of biaxial nematics

Biaxial nematic (N(b)) liquid crystals are a fascinating condensed matter phase that has baffled, for more than thirty years, scientists engaged in the challenge of demonstrating its actual existence, and which has only recently been experimentally found. During this period computer simulations of model N(b) have played an important role, both in providing the basic physical properties to be expected from these systems, and in giving clues about the molecular features essential for the thermodynamic stability of N(b) phases. However, simulation studies are expected to be even more crucial in the future for unravelling the structural features of biaxial mesogens at the molecular level, and for helping in the design and optimization of devices towards the technological deployment of N(b) materials. This review article gives an overview of the simulation work performed so far, and relying on the recent experimental findings, focuses on the still unanswered questions which will determine the future challenges in the field.

Field Response and Switching Times in Biaxial Nematics

We study by means of virtual molecular dynamics computer experiments the response of a bulk biaxial nematic to an applied external field and, in particular, the relative speed of reorientation of the principal director axis and of the secondary one, typical of these new materials, upon a pi2 field switch. We perform the simulations setting up and integrating the equations of motion for biaxial Gay-Berne particles using quaternions and a suitable time reversible symplectic integrator. We find that switching of the secondary axis is up to an order of magnitude faster than that of the principal axis, and that under fields above a certain strength a reorganization of local domains, temporarily disrupting the nematic and biaxial ordering, rather than a collective concerted reorientation occurs.

Theoretical Characterization of the Structural and Hole Transport Dynamics in Liquid-Crystalline Phthalocyanine Stacks

We present a joint molecular dynamics (MD)/kinetic Monte Carlo (KMC) study aimed at the atomistic description of charge transport in stacks of liquid-crystalline tetraalkoxy-substituted, metal-free phthalocyanines. The molecular dynamics simulations reproduce the major structural features of the mesophases, in particular, a phase transition around 340 K between the rectangular and hexagonal phases. Charge transport simulations based on a Monte Carlo algorithm show an increase by 2 orders of magnitude in the hole mobility when accounting for the rotational and translational dynamics. The results point to the formation of dynamical structural defects along the columns.

Assemblies of perylene diimide derivatives with melamine into luminescent hydrogels

We report unique and spontaneous formation of hydrogels of perylene derivatives with melamine. The luminescent gel network is formed by H-type aggregation of the perylene core, supramolecularly cross-linked by melamine units. As a result of controlled aggregation in the extended nanofibers, strong exciton fluorescence emission is observed.

Simulation of Vapor‐Phase Deposition and Growth of a Pentacene Thin Film on C60 (001)

Current research in organic electronics is clearly evidencing that the strive to produce efficient organic electronic devices requires high performance materials that can only be realized through a rational design [Special11]. Although polymer-based systems are at the moment the most appealing for market applications, mainly because of their solution processability, small molecule-based devices possess potential for commercialization, presenting comparable performances and a better batch-to-batch reproducibility of their properties [Walker11]. The interest in small molecules of well defined crystalline structure arises also from the fine control over final morphologies that can be achieved through vapour-phase growth techniques [Ruiz04, Rolin10], control that allows, with respect to polymer devices, a deeper understanding of the structure-electronic properties relationships. Indeed building an efficient electronic device (e. g. a solar cell) coincides to a large extent with the fine tuning of the electronic properties at the different interfaces, typically metal-organic, inorganic-organic, and organic-organic. In this communication we focus on the latter interface between two of the most studied p-and n-type molecular organic semiconductors, pentacene (A5) and C 60 fullerene. These materials have been recently employed in producing rather efficient thin film bilayer solar cells [Yoo04, Mayer04, Yoo07, Cheyns07, Dissanayake07], ambipolar field effect transistors [Kuwahara04, Yan09, Cosseddu10] and low-voltage-operating organic complementary inverters [Na09]. The relative simplicity and the good performances of C 60 /A5 heterojunctions has stimulated theoretical research on the electronic processes occurring at the interface: density functional theory [Yi09], valence-bond Hartree-Fock [Linares10] and microelectrostatic calculations [Verlaak09] have been employed in studying model interfaces of increasing complexity. These studies coherently underline the importance of relative molecular orientations and positions in determining the interface dipole and electronic couplings, i.e. the key factors governing exciton transport and fission, charge generation and separation [Rao10]. This in turn means that improving computational predictions of the molecular organization at the interface is fundamental to understanding experimental systems of great interest. This task can in principle be tackled by using classical atomistic force fields, but it is definitely not a straightforward one. Indeed, it has been recently recognized that molecular organizations at the interface depend on the preparation process and not just on thermodynamic state of the system, so that imitating the experimental preparation techniques is often necessary to produce realistic morphologies [Liu08, Cheung08, MacKenzie10, Clancy11, Beljonne11]. For this specific system, Clancy and co-workers applied classical simulations at both coarse-grained [Choudhary06] and atomistic detail [Goose07] to study some aspects of the pentacene …

Exploring the Energy Landscape of the Charge Transport Levels in Organic Semiconductors at the Molecular Scale

The extraordinary semiconducting properties of conjugated organic materials continue to attract attention across disciplines including materials science, engineering, chemistry, and physics, particularly with application to organic electronics. Such materials are used as active components in light-emitting diodes, field-effect transistors, or photovoltaic cells, as a substitute for (mostly Si-based) inorganic semiconducting materials. Many strategies developed for inorganic semiconductor device building (doping, p-n junctions, etc.) have been attempted, often successfully, with organics, even though the key electronic and photophysical properties of organic thin films are fundamentally different from those of their bulk inorganic counterparts. In particular, organic materials consist of individual units (molecules or conjugated segments) that are coupled by weak intermolecular forces. The flexibility of organic synthesis has allowed the development of more efficient opto-electronic devices including impressive improvements in quantum yields for charge generation in organic solar cells and in light emission in electroluminescent displays. Nonetheless, a number of fundamental questions regarding the working principles of these devices remain that preclude their full optimization. For example, the role of intermolecular interactions in driving the geometric and electronic structures of solid-state conjugated materials, though ubiquitous in organic electronic devices, has long been overlooked, especially when it comes to these interfaces with other (in)organic materials or metals. Because they are soft and in most cases disordered, conjugated organic materials support localized electrons or holes associated with local geometric distortions, also known as polarons, as primary charge carriers. The spatial localization of excess charges in organics together with low dielectric constant (ε) entails very large electrostatic effects. It is therefore not obvious how these strongly interacting electron-hole pairs can potentially escape from their Coulomb well, a process that is at the heart of photoconversion or molecular doping. Yet they do, with near-quantitative yield in some cases. Limited screening by the low dielectric medium in organic materials leads to subtle static and dynamic electronic polarization effects that strongly impact the energy landscape for charges, which offers a rationale for this apparent inconsistency. In this Account, we use different theoretical approaches to predict the energy landscape of charge carriers at the molecular level and review a few case studies highlighting the role of electrostatic interactions in conjugated organic molecules. We describe the pros and cons of different theoretical approaches that provide access to the energy landscape defining the motion of charge carriers. We illustrate the applications of these approaches through selected examples involving OFETs, OLEDs, and solar cells. The three selected examples collectively show that energetic disorder governs device performances and highlights the relevance of theoretical tools to probe energy landscapes in molecular assemblies.

Charge Dissociation at Interfaces between Discotic Liquid Crystals: The Surprising Role of Column Mismatch

The semiconducting and self-assembling properties of columnar discotic liquid crystals have stimulated intense research toward their application in organic solar cells, although with a rather disappointing outcome to date in terms of efficiencies. These failures call for a rational strategy to choose those molecular design features (e.g., lattice parameter, length and nature of peripheral chains) that could optimize solar cell performance. With this purpose, in this work we address for the first time the construction of a realistic planar heterojunction between a columnar donor and acceptor as well as a quantitative measurement of charge separation and recombination rates using state of the art computational techniques. In particular, choosing as a case study the interface between a perylene donor and a benzoperylene diimide acceptor, we attempt to answer the largely overlooked question of whether having well-matching donor and acceptor columns at the interface is really beneficial for optimal charge separation. Surprisingly, it turns out that achieving a system with contiguous columns is detrimental to the solar cell efficiency and that engineering the mismatch is the key to optimal performance.