Solid-State Effects on the Optical Excitation of Push-Pull Molecular J-Aggregates by First-Principles Simulations

J-aggregates are a class of low-dimensional molecular crystals which display enhanced interaction with light. These systems show interesting optical properties as an intense and narrow red-shifted absorption peak (J-band) with respect to the spectrum of the corresponding monomer. The need to theoretically investigate optical excitations in J-aggregates is twofold: a thorough first-principles description is still missing and a renewed interest is rising recently in understanding the nature of the J-band, in particular regarding the collective mechanisms involved in its formation. In this work, we investigate the electronic and optical properties of a J-aggregate molecular crystal made of ordered arrangements of organic push-pull chromophores. By using a time dependent density functional theory approach, we assess the role of the molecular packing in the enhancement and red shift of the J-band along with the effects of confinement in the optical absorption, when moving from bulk to low-dimensional crystal structures. We simulate the optical absorption of different configurations (i.e., monomer, dimers, a polymer chain, and a monolayer sheet) extracted from the bulk crystal. By analyzing the induced charge density associated with the J-band, we conclude that it is a longitudinal excitation, delocalized along parallel linear chains and that its overall red shift results from competing coupling mechanisms, some giving red shift and others giving blue shift, which derive from both coupling between transition densities and renormalization of the single-particle energy levels.Comment: This is the published version of the work, distributed under the terms of the ACS AuthorChoice licence https://pubs.acs.org/page/policy/authorchoice_termsofuse.htm

Quantifying the Plasmonic Character of Optical Excitations in a Molecular J-Aggregate

The definition of plasmon at the microscopic scale is far from being understood. Yet, it is very important to recognize plasmonic features in optical excitations, as they can inspire new applications and trigger new discoveries by analogy with the rich phenomenology of metal nanoparticle plasmons. Recently, the concepts of plasmonicity index and the generalized plasmonicity index (GPI) have been devised as computational tools to quantify the plasmonic nature of optical excitations. The question may arise whether any strong absorption band, possibly with some sort of collective character in its microscopic origin, shares the status of plasmon. Here we demonstrate that this is not always the case, by considering a well-known class of systems represented by J-aggregates molecular crystals, characterized by the intense J band of absorption. By means of first-principles simulations, based on a many-body perturbation theory formalism, we investigate the optical properties of a J-aggregate made of push-pull organic dyes. We show that the effect of aggregation is to lower the GPI associated with the J-band with respect to the isolated dye one, which corresponds to a nonplasmonic character of the electronic excitations. In order to rationalize our finding, we then propose a simplified one-dimensional theoretical model of the J-aggregate. A useful microscopic picture of what discriminates a collective molecular crystal excitation from a plasmon is eventually obtained.Comment: Published by ACS under ACS AuthorChoice licens

Interplay between Intra- and Intermolecular Charge Transfer in the Optical Excitations of J-Aggregates

In a first-principles study based on density functional theory and many-body perturbation theory, we address the interplay between intra- and intermolecular interactions in a J-aggregate formed by push-pull organic dyes by investigating its electronic and optical properties. We find that the most intense excitation dominating the spectral onset of the aggregate, i.e., the J-band, exhibits a combination of intramolecular charge transfer, coming from the push-pull character of the constituting dyes, and intermolecular charge transfer, due to the dense molecular packing. We also show the presence of a pure intermolecular charge-transfer excitation within the J-band, which is expected to play a relevant role in the emission properties of the J-aggregate. Our results shed light on the microscopic character of optical excitations of J-aggregates and offer new perspectives to further understand the nature of collective excitations in organic semiconductors.Comment: published under ACS Authorchoice licens

Immediate versus delayed loading: comparison of primary stability loss after miniscrew placement in orthodontic patients-a single-centre blinded randomized clinical trial

Introduction: The aim of this randomized clinical trial was to compare torque recordings at insertion time and 1 week post-placement between immediately loaded orthodontic miniscrews and an unloaded control group. Trial design: This RCT was designed as parallel with an allocation ratio of 1:1. Methods: Eligibility criteria to enroll patients were: needs of fixed orthodontic treatment, no systemic disease, absence of using drugs altering bone metabolism. All patients were consecutively treated in a private practice and the miniscrews were placed by the same author. Patients received ORTHOImplant (3M Unitek) miniscrews and they were blindly divided in two groups: group 1 screws were unloaded between T0 and T1, group 2 received immediately loaded screws with NiTi coil. For each patient, maximum insertion torque (MIT) was evaluated at T0. After 1 week, without loading, the screw torque was measured again (T1) and at the end of the treatment maximal removal torque was evaluated (T2). Torque variation in the first week was considered as the primary outcome. Randomization: A randomization list was created for the group assignment, with an allocation ratio of 1:1. Blinding: The study was single blinded in regard of the statistical analysis. Results: Patients enrolled in the clinical trial were 51 for a total of 81 miniscrews. The recruitment started in November 2012 and the observation period ended in August 2014. Twenty-six and twenty-five patients were analysed in group 1 and 2, respectively. The MIT mean in each placement time was 18.25 Ncm (SD = 3.00), 11.41 Ncm (SD = 3.51) and 10.52 Ncm (SD = 5.14) at T0, T1, and T2 time, respectively. In group 1, the torque decrease between T1 and T0 was statistically higher compared to group 2 (P value = 0.003). Statistically significant effects of the placement times on MIT were found (P value <0.0001). No serious harm was observed. Limitations: This study was performed using only direct force on the miniscrew and not using the miniscrew as an indirect anchorage. It was not possible to obtain quantitative data on bone quality or root proximity to miniscrews. Conclusions: A significant stability loss was observed in the first week in both groups; Group 1 showed a statistically higher torque loss in the first week when compared to the immediately loaded group. There were statistically significant effects of the measurement times on MIT and of the miniscrew location on MIT. The overall failure rate was 7.4%. Trial registration: This trial was not registered. Protocol: The protocol was not published before trial commencement

Accurate ab initio tight-binding Hamiltonians: Effective tools for electronic transport and optical spectroscopy from first principles

The calculations of electronic transport coefficients and optical properties require a very dense interpolation of the electronic band structure in reciprocal space that is computationally expensive and may have issues with band crossing and degeneracies. Capitalizing on a recently developed pseudoatomic orbital projection technique, we exploit the exact tight-binding representation of the first-principles electronic structure for the purposes of (i) providing an efficient strategy to explore the full band structure E-n (k), (ii) computing the momentum operator differentiating directly the Hamiltonian, and (iii) calculating the imaginary part of the dielectric function. This enables us to determine the Boltzmann transport coefficients and the optical properties within the independent particle approximation. In addition, the local nature of the tight-binding representation facilitates the calculation of the ballistic transport within the Landauer theory for systems with hundreds of atoms. In order to validate our approach we study the multivalley band structure of CoSb3 and a large core-shell nanowire using the ACBN0 functional. In CoSb3 we point the many band minima contributing to the electronic transport that enhance the thermoelectric properties; for the core-shell nanowire we identify possible mechanisms for photo-current generation and justify the presence of protected transport channels in the wire

Extending cervicoplastic surgery: an alternative technique to overcome the limitation of office hysteroscopy

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aflow.org: A Web Ecosystem of Databases, Software and Tools

To enable materials databases supporting computational and experimental research, it is critical to develop platforms that both facilitate access to the data and provide the tools used to generate/analyze it - all while considering the diversity of users' experience levels and usage needs. The recently formulated FAIR principles (Findable, Accessible, Interoperable, and Reusable) establish a common framework to aid these efforts. This article describes aflow_org, a web ecosystem developed to provide FAIR - compliant access to the AFLOW databases. Graphical and programmatic retrieval methods are offered, ensuring accessibility for all experience levels and data needs. aflow_org goes beyond data-access by providing applications to important features of the AFLOW software, assisting users in their own calculations without the need to install the entire high-throughput framework. Outreach commitments to provide AFLOW tutorials and materials science education to a global and diverse audiences will also be presented.Comment: 32 pages, 8 figure