arXiv subjects

Matteo Tommasini

Publications and source records attributed to Matteo Tommasini.

15 recordsLinked to original sources

arXiv2025

Wettability and sp2/sp3 ratio effects on supercapacitor performance of N-doped hydrogenated amorphous Carbon Nanofoam

Pulsed laser-deposited amorphous carbon nanofoams are potential candidate for electrochemical energy storage applications due to ultra-light weight, large volumetric void fractions, and co-existence of sp, sp2 and sp3 carbon hybridization. It is known that charge storage in carbon nanostructures containing disordered sp2-domains is determined by their wettability, surface area, and porosity. However, their charge-storage performance is limited to the areal capacitance of the order of a few mF/cm2. We enhanced the supercapacitor performance of nitrogen-doped amorphous carbon nanofoam by engineering its wettability and sp2-C/sp3-C ratio by vacuum annealing. The specific capacitance was enhanced by about fifty times and the device voltage increased from 0.8 to 1.1 V compared to as-grown carbon nanofoam. In addition, we examined for the first time the initial increase in specific capacitance of the aqueous symmetric supercapacitor with respect to the scan rate, employing in-situ measurements coupling Raman spectroscopy and electrochemistry. We attribute this effect, observed but generally not explained in previous works in the literature, to the electrochemical activation induced by structural changes during the charge storage performance. This optimization of pulsed laser deposited carbon nanofoam may open an avenue for fabricating lightweight and porous nanostructures for advanced macro-to-micro-supercapacitor devices.

cond-mat.mtrl-sci↗

arXiv2021

Vibrational and nonlinear optical properties of amine-capped push-pull polyynes by infrared and Raman spectroscopy

The vibrational properties of a series of push-pull polyynes have been studied by infrared and Raman spectroscopy. The simultaneous activation of a strong infrared and Raman mode, i.e. the collective vibration of CC bonds of the sp carbon chain, highlights the effectiveness of a polyyne bridge in promoting charge transfer between the electron donor (D) and acceptor (A) ends, thus suggesting that ad-hoc functionalized polyynes are worth being explored as building blocks of organic materials with attractive first-order optical nonlinearity. The optical, electronic, and vibrational properties of these molecules have been investigated with the support of density functional theory calculations, as well as the electronic and vibrational first hyperpolarizabilities ($β$). The mid-low region of the IR spectra (800-1600 cm$^{-1}$) has been analyzed in detail, searching for marker bands of the specific terminations of the different sp carbon chains thus achieving a complete vibrational characterization of sp hybridized push-pull systems.

cond-mat.mes-hall↗

arXiv2021

Topology-dependent conjugation effects in graphdiyne molecular fragments

Graphdiynes (GDYs) as two-dimensional carbon structures based on sp2 hybridized aromatic rings connected by sp-hybridized acetylenic linear links are gathering an increasing popularity, both for their peculiar properties and for the promising applications. In these materials, structural features affect the degree of pi-electron conjugation resulting in different electronic, optical and vibrational properties. In particular, how topology, connectivity between sp and sp2 domains and system size are related with the final properties is fundamental to understand structure-property relationships and to tailor the properties by proper structure design. By using a computational approach based on density functional theory calculations, we here investigate structure-property relations in a class of 1D and 2D GDY molecular fragments as building block models of extended structures. By analysing how the structure can modulate the pi-electron conjugation in these systems, HOMO-LUMO gap is found to depend on the peculiar topology and connections between linear sp domains and aromatic units. A topological indicator is computed, showing a trend with the gap and with the frequency of the main vibrational mode occurring in Raman spectra. Our findings can contribute to guide the molecular design of new GDY-based sp-sp2 carbon materials, aiming at tuning their properties by precise control of the structure.

cond-mat.mtrl-sci↗

arXiv2020

Raman and IR spectra of graphdiyne nanoribbons

γ-graphdiyne is a 2D carbon structure beyond graphene: it is formed by sp and sp2 carbon atoms organized as hexagonal rings connected by linear links, and it is predicted to be a semiconductor. The lateral confinement of γ-graphdiyne nanoribbons significantly affects the electronic and vibrational properties. By means of periodic Density Functional Theory (DFT) calculations we investigate here the electronic band structure, the Raman and IR spectra of the γ-graphdiyne 2D crystal and related nanoribbons. We discuss the effect of the functional and basis set on the evaluation of the band gap, highlighting the reliability of hybrid functionals. By joining DFT calculations with a symmetry analysis, we assign in detail the IR and Raman spectra of γ-graphdiyne. On this basis we show the modulation of the gap in nanoribbons of increasing width and different edges (armchair, zigzag). We assess how confinement affects the Raman and IR spectra of such nanoribbons by comparing their vibrational modes with the phonons of the parent 2D crystal. Our symmetry-based classification allows identifying the marker bands sensitive to the edge structure and lateral confinement of nanoribbons of increasing width. These results show the effectiveness of vibrational spectroscopy for the characterization of such nanostructures.

cond-mat.mes-hall↗

arXiv2019

Size-selected polyynes synthesized by submerged arc discharge in water

Polyynes are linear sp-carbon chains of finite length consisting in a sequence of alternated single and triple bonds and displaying appealing optical and electronic properties. A simple, low cost and scalable production technique for polyynes is the submerged arc discharge (SAD) in liquid, which so far, has been mainly exploited in organic solvents. In this work, we investigated in detail SAD in water as a cheap and non-toxic solvent for the production of polyynes. The role of process parameters such as current (10-25 A) and voltage (20-25 V) in the production yield have been investigated, as well as polyynes stability. Polyynes terminated by hydrogen (CnH2: n=6-16) were identified by High-Performance Liquid Chromatography (HPLC) coupled with UV-Visible absorption spectroscopy and with the support of density functional theory (DFT) calculations. Size-selected polyynes separated by HPLC were analyzed by surface enhanced Raman spectroscopy (SERS). The formation process was monitored by in situ SERS using an immersed fiber-optic Raman probe and employing Ag nanoparticles directly produced in the solution by SAD.

cond-mat.mtrl-sci↗

arXiv2019

Plasmonic superchiral lattice resonances in the mid-infrared

Recent efforts in the field of surface-enhanced spectroscopies have focused on the paradigm of superchirality, entailing the engineering of the local electromagnetic fields to boost the enantiospecific interaction between light and chiral molecules. In this framework, approaches based on both metallic and dielectric nanostructures have been proposed and have also recently been extended to vibrational circular dichroism in the mid-infrared. In this work, we design, fabricate and characterize arrays of chiral plasmonic slits featuring enhanced chiral fields in the mid-infrared. We exploit collective lattice resonances to further enhance the local intensity and to generate sharp features in the circular dichroism spectra of the platform. Such features are ideally suited to test the superchiral coupling with the vibrational resonances of chiral molecules.

cond-mat.mes-hall↗

arXiv2017

Atlases for Ineffective Orbifolds

We give a definition of atlases for ineffective orbifolds, and prove that this definition leads to the same notion of orbifold as that defined via topological groupoids.

math.CT↗

arXiv2016

Semiconductor-to-metal transition in carbon-atom wires driven by sp2 conjugated endgroups

Novel bis(biphenyl)-capped polyynes have been synthesized to investigate the modulation of the electronic and optical properties of sp-hybridized carbon-atom wires (CAWs) capped with π-conjugated $sp^{2}$ endgroups. Raman and Surface Enhanced Raman spectroscopy (SERS) investigation of these systems and Density Functional Theory (DFT) calculations reveal structural changes from polyyne-like with alternating single-triple bonds towards cumulene-like with more equalized bonds as a consequence of the charge transfer occurring when wires interact with metallic nanoparticles. While polyynes have semiconducting electronic properties, a more equalized system tends to a cumulene-like structure characterized by a nearly metallic behavior. The possibility to drive a semiconductor-to-metal transition has been investigated by systematic DFT calculations on a series of CAWs capped with different conjugated endgroups revealing that the modulation of the structural, electronic and vibrational properties of the sp-carbon chain towards the metallic wire cannot be simply obtained by using extended π-conjugated $sp^{2}$ carbon endgroups, but require a suitable chemical design of the endgroup and control of charge transfer. These results provide useful guidelines for the design of novel $sp-sp^2$ hybrid carbon nanosystems with tunable properties, where graphene-like and polyyne-like domains are closely interconnected. The capability to tune the final electronic or optical response of the material makes these hybrid $sp-sp^2$ systems appealing for a future all-carbon-based science and technology.

cond-mat.mes-hall↗

arXiv2016

Some insights on bicategories of fractions: representations and compositions of 2-morphisms

In this paper we investigate the construction of bicategories of fractions originally described by D. Pronk: given any bicategory $\mathcal{C}$ together with a suitable class of morphisms $\mathbf{W}$, one can construct a bicategory $\mathcal{C}[\mathbf{W}^{-1}]$, where all the morphisms of $\mathbf{W}$ are turned into internal equivalences, and that is universal with respect to this property. Most of the descriptions leading to this construction were long and heavily based on the axiom of choice. In this paper we considerably simplify the description of the equivalence relation on $2$-morphisms and the constructions of associators, vertical and horizontal compositions in $\mathcal{C}[\mathbf{W}^{-1}]$, thus proving that the axiom of choice is not needed under certain conditions. The simplified description of associators and compositions will also play a crucial role in two forthcoming papers about pseudofunctors and equivalences between bicategories of fractions.

math.CT↗

arXiv2015

A bicategory of reduced orbifolds from the point of view of differential geometry - I

We describe a bicategory $(\mathcal{R}ed\,\mathcal{O}rb)$ of reduced orbifolds in the framework of classical differential geometry (i.e. without any explicit reference to notions of Lie groupoids or differentiable stacks, but only using orbifold atlases, local lifts and changes of charts). In order to construct such a bicategory, we first define a $2$-category $(\mathcal{R}ed\,\mathcal{A}tl)$ whose objects are reduced orbifold atlases (on any paracompact, second countable, Hausdorff topological space). The definition of morphisms is obtained as a slight modification of a definition by A. Pohl, while the definitions of $2$-morphisms and compositions of them is new in this setup. Using the bicalculus of fractions described by D. Pronk, we are able to construct the bicategory $(\mathcal{R}ed\,\mathcal{O}rb)$ from the $2$-category $(\mathcal{R}ed\,\mathcal{A}tl)$. We prove that $(\mathcal{R}ed\,\mathcal{O}rb)$ is equivalent to the bicategory of reduced orbifolds described in terms of proper, effective, étale Lie groupoids by D. Pronk and I. Moerdijk and to the $2$-category of reduced orbifolds described by several authors in the past in terms of a suitable class of differentiable Deligne-Mumford stacks.

math.CT↗

arXiv2014

Weak fiber products in a bicategory of fractions

We fix any pair $(\mathbf{\mathscr{C}},\mathbf{W})$ consisting of a bicategory and a class of morphisms in it, admitting a bicalculus of fractions, i.e. a "localization" of $\mathbf{\mathscr{C}}$ with respect to the class $\mathbf{W}$. In the resulting bicategory of fractions, we identify necessary and sufficient conditions for the existence of weak fiber products.

math.CT↗

arXiv2014

Some insights on bicategories of fractions - II

We fix any bicategory $\mathscr{A}$ together with a class of morphisms $\mathbf{W}_{\mathscr{A}}$, such that there is a bicategory of fractions $\mathscr{A}[\mathbf{W}_{\mathscr{A}}^{-1}]$. Given another such pair $(\mathscr{B},\mathbf{W}_{\mathscr{B}})$ and any pseudofunctor $\mathcal{F}:\mathscr{A}\rightarrow\mathscr{B}$, we find necessary and sufficient conditions in order to have an induced pseudofunctor $\mathcal{G}:\mathscr{A}[\mathbf{W}_{\mathscr{A}}^{-1}]\rightarrow \mathscr{B}[\mathbf{W}_{\mathscr{B}}^{-1}]$. Moreover, we give a simple description of $\mathcal{G}$ in the case when the class $\mathbf{W}_{\mathscr{B}}$ is "right saturated".

math.CT↗

arXiv2014

Some insights on bicategories of fractions - III

We fix any bicategory $\mathscr{A}$ together with a class of morphisms $\mathbf{W}_{\mathscr{A}}$, such that there is a bicategory of fractions $\mathscr{A}[\mathbf{W}_{\mathscr{A}}^{-1}]$. Given another such pair $(\mathscr{B},\mathbf{W}_{\mathscr{B}})$ and any pseudofunctor $\mathcal{F}:\mathscr{A}\rightarrow\mathscr{B}$, we find necessary and sufficient conditions in order to have an induced equivalence of bicategories from $\mathscr{A}[\mathbf{W}_{\mathscr{A}}^{-1}]$ to $\mathscr{B}[\mathbf{W}_{\mathscr{B}}^{-1}]$. In particular, this gives necessary and sufficient conditions in order to have an equivalence from any bicategory of fractions $\mathscr{A}[\mathbf{W}_{\mathscr{A}}^{-1}]$ to any given bicategory $\mathscr{B}$.

math.CT↗

arXiv2012

Universal families of extensions of coherent systems

We prove a result of cohomology and base change for families of coherent systems over a curve. We use that in order to prove the existence of (non-split, non-degenerate) universal families of extensions for families of coherent systems (in the spirit of the paper "Universal families of extensions" by H. Lange). Such results will be applied in subsequent papers in order to describe the wallcrossing for some moduli spaces of coherent systems.

math.AG↗

arXiv2010

Orbifolds and groupoids

We define a 2-category structure (Pre-Orb) on the category of reduced complex orbifold atlases. We construct a 2-functor F from (Pre-Orb) to the 2-category (Grp) of proper étale effective groupoid objects over the complex manifolds. Both on (Pre-Orb) and (Grp) there are natural equivalence relations on objects: (a natural extension of) equivalence of orbifold atlases in (Pre-Orb) and Morita equivalences in (Grp). We prove that F induces a bijection between the equivalence classes of its source and target.

math.AT↗