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An innovative method to quantitatively assess the state of degradation of paper in a non-destructive way has been developed by using THz time-domain spectroscopy (THz-TDS). The method relies on the observation that the hydrolytic and oxidative degradation of cellulose in paper is accompanied with rearrangement of the hydrogen bonds (H-bond) network of cellulose polymers. This gives clear fingerprints in the THz spectral profiles. THz-TDS is a suitable approach to study low-energy vibrational properties of biological materials in a non-destructive way. The THz photon energy range (about 1-40 meV) is particularly suitable to probe the H-bonds between molecules. However, the quantitative assessment of the state of preservation of artworks poses significant challenges, in particular when measurements on low refractive index and thin samples, such as ancient documents and drawings, must be carried out [1]. In the present study, we have successfully solved this problem obtaining a precise determination of the absorption by cellulose fibers in the 0.2-3.5 THz (7-117cm-1) range in single freely standing paper sheets. This has been achieved by developing a new procedure to remove from the experimental signals the spurious interference effects generated by the Fabry-Pérot resonances in the sheet. By using this approach, the THz absorption coefficient of cellulose fibers in ancient and modern samples artificially aged has been obtained. The THz absorption spectra are explained in terms of absorption peaks of the cellulose crystalline phase superimposed to a background contribution due to a disordered H-bonds network [2]. The complex evolution of the spectra as a function of natural and artificial aging is explained with a reduction up to 30% of the H-bond density in the cellulose polymer networks and a parallel increasing of the sample crystallinity evident in the peaks at about 2.1 and 3.1 THz. The comparison with density functional theory ab-initio calculations suggests that the observed THz spectral changes could be related not only to the recrystallization of amorphous regions, but also to the progressive degradation of the external surfaces of crystalline domains. These results demonstrate a significant potential in the non-destructive analysis of the structural modifications of cellulose and paper artifacts by aging, resulting, at a macroscopic scale, in a progressive weakening of the mechanical properties of paper [3]. [1] T. Trafela, M. Mizuno, K. Fukunaga, and M. Strlic, Appl. Phys. A, 111, 2013, 83-90. [2] E. Scarpellini, M. Ortolani, A. Nucara, L. Baldassarre, M. Missori, R. Fastampa, and R. Caminiti, J. Phys. Chem. C 120, 2016, 24088-24097. [3] L. Teodonio, M. Missori, D. Pawcenisc, J. ?ojewskac, F. Valle, Micron 91, 2016, 75-81.

We present a first principles study of the stability, and of the electronic and optical properties of graphene with nitrogen doped vacancies. Moreover, we use the vacancies as anchoring sites for Mg, Zn, Pd al Pt atoms and vary the concentration of defects. Decoration of the defects with metal atoms produces semi-metallic systems for any studied size of the cell, with linear bands crossing at the Fermi level. The peculiar electronic properties of massless Dirac fermions in graphene are hence kept, although with anisotropic Fermi velocities. New sharp peaks appear in the optical conductivity in the visible range, thus strongly enhancing the optical response of graphene.

Highly oriented pyrolitic graphite (HOPG) is an inert substrate with a structural honeycomb lattice, well suited for the growth of two-dimensional (2D) silicene layer. It was reported that when Si atoms are deposited on HOPG surface at room temperature, they arrange in two configurations: silicene nanosheets and three dimensional clusters. In this work we demonstrate, by using scanning tunneling microscopy (STM) and Raman spectroscopy, that a third configuration stabilizes in the form of Si 2D nanosheets intercalated below the first top layer of carbon atoms. The Raman spectra reveal a structure located at 538 cm$^{-1}$ which we ascribe to the presence of sp$^2$ Si hybridization. Moreover, the silicon deposition induces several modifications in the graphite D and G Raman modes, which we interpret as an experimental evidence of the intercalation of the silicene nanosheets. The Si atom intercalation at room temperature takes place at the HOPG step edges and it detaches only the outermost graphene layer inducing a strong tensile strain mainly concentrated on the edges of the silicene nanosheets. Theoretical calculations of the structure and energetic viability of the silicene nanosheets, of the strain distribution on the outermost graphene layer and its influence on the Raman resonances support the STM and Raman observations., 18 pages, 9 figures, 2 tables

Using density-functional and many-body perturbation theory, we study the electronic, optical, and excitonic properties of indium nitride as single monolayer and bilayer in comparison with the bulk phase. We investigate the stable geometry for the monolayer, the graphenelike unbuckled honeycomb structure, and for the bilayer the AA' stacking geometry. We demonstrate that the quasiparticle and optical gaps, going from bulk to two-dimensional systems, open dramatically due to strong quantum confinement and reduced screening. Large excitonic effects, which survive at room temperature, are predicted. Our results suggest that low-dimensional InN is a promising material for optoelectronic devices in the visible to near-infrared spectral ranges varying with the number of atomic layers and light propagation.

We propose a characterization tool for studies of the band structure of new materials promising for the observation of topological phase transitions. We show that a specific resonant feature in the entropy per electron dependence on the chemical potential may be considered as a fingerprint of the transition between topological and trivial insulator phases. The entropy per electron in a honeycomb two-dimensional crystal of germanene subjected to the external electric field is obtained from the first principle calculation of the density of electronic states and the Maxwell relation. We demonstrate that, in agreement to the recent prediction of the analytical model, strong spikes in the entropy per particle dependence on the chemical potential appear at low temperatures. They are observed at the values of the applied bias both below and above the critical value that corresponds to the transition between the topological insulator and trivial insulator phases, while the giant resonant feature in the vicinity of zero chemical potential is strongly suppressed at the topological transition point, in the low temperature limit. In a wide energy range, the van Hove singularities in the electronic density of states manifest themselves as zeros in the entropy per particle dependence on the chemical potential., Comment: 8 pages, 5 figures; final version published in PRB

We report on Raman scattering of GaSe for thicknesses varying from bulk down to bilayer. The Raman spectra using 532 nm excitation show a strong dependence on layer thickness. The two out-of-plane modes of GaSe shift in opposite directions as the thickness increases. However, from pentalayer the Raman spectra of GaSe do not show any further change thus reaching bulk nature in terms of optical properties. We also perform ab initio density functional theory calculations for the geometry, the electronic band structure, and the Raman frequencies for bulk down to one monolayer. Good agreement with the experimental results is found, and we reproduce the trend, driven by the number of layers, in the Raman shifts. Our results present the first systematic approach to a layer dependent Raman study of GaSe and answer contradictions reported in the literature.

Using a combination of the density functional theory and tight-binding calculations, we study electronic and optical properties of asymmetric chevron-type graphene nanoribbons recently synthesized with atomic precision. We demonstrate that the low-energy optical selection rules in such infinite chiral ribbons are more reminiscent of those for zigzag rather than for armchair ribbons. It is also shown that, starting from about 25 nm long ribbons, the low-energy absorption and therefore the selection rules of infinitely long ribbons are well reproduced in the finite cluster approach. Hence, ribbons longer than 25 nm (about 28 unit cells) can be treated as infinitely long ones.

We review the behavior of the entropy per particle in various two-dimensional electronic systems. The entropy per particle is an important characteristic of any many body system that tells how the entropy of the ensemble of electrons changes if one adds one more electron. Recently, it has been demonstrated how the entropy per particle of a two-dimensional electron gas can be extracted from the recharging current dynamics in a planar capacitor geometry. These experiments pave the way to the systematic studies of entropy in various crystal systems including novel two-dimensional crystals such as gapped graphene, germanene and silicene. Theoretically, the entropy per particle is linked to the temperature derivative of the chemical potential of the electron gas by the Maxwell relation. Using this relation, we calculate the entropy per particle in the vicinity of topological transitions in various two-dimensional electronic systems. We show that the entropy experiences quantized steps at the points of Lifshitz transitions in a two-dimensional electronic gas with a parabolic energy spectrum. In contrast, in doubled-gapped Dirac materials, the entropy per particles demonstrates characteristic spikes once the chemical potential passes through the band edges. The transition from a topological to trivial insulator phase in germanene is manifested by the disappearance of a strong zero-energy resonance in the entropy per particle dependence on the chemical potential. We conclude that studies of the entropy per particle shed light on multiple otherwise hidden peculiarities of the electronic band structure of novel two-dimensional crystals., Comment: 33 pages,15 figures. Accepted for publication in JETP. arXiv admin note: text overlap with arXiv:1803.02083, arXiv:1712.09118, arXiv:1703.08962, arXiv:1512.08450

Slightly buckled, graphene-like honeycomb crystals made by silicon, silicene, or by other group-IV elements such as germanene and stanene represent atomically thin films, i.e., two-dimensional (2D) systems. The theoretical description of their optical properties suffers from three difficulties, (i) a thickness much smaller than the wavelength of light, (ii) their common modeling by superlattice arrangements with sufficiently large layer distances, and (iii) the inclusion of many-body effects. Here, the solutions of all problems are discussed. (i) The optical response of an individual honeycomb crystal is described by a tensor of 2D optical conductivities or dielectric functions, which are related to the optical response of the corresponding superlattice. (ii) The influence of such a sheet crystal on the transmittance, reflectance and absorbance of a layer system is described. (iii) Excitonic and quasiparticle effects are demonstrated to widely cancel each other. Silicene sheets are investigated in detail. As a consequence of the linear bands and Dirac cones the low-frequency absorbance is defined by the Sommerfeld finestructure constant. Van Hove singularities represented by critical points in the interband structure are identified at higher photon energies. Clear chemical trends along the row C \(\rightarrow \) Si \(\rightarrow \) Ge \(\rightarrow \) Sn are derived. The influence of multiple layers is studied for the cases of bilayer silicene and graphene.

The exotic electrodynamics properties of graphene come from the linearly dispersive electronic bands that host massless Dirac electrons. A similar behavior was predicted to manifest in freestanding silicene, the silicon counterpart of graphene, thereby envisaging a new route for silicon photonics. However, the access to silicene exploitation in photonics was hindered so far by the use of optically inappropriate substrates in experimentally realized silicene. Here we report on the optical conductivity of silicon nanosheets epitaxially grown on optically transparent Al2O3(0001) from a thickness of a few tens of nanometers down to the extreme two-dimensional (2D) limit. When a 2D regime is approached, a Dirac-like electrodynamics can be deduced from the observation of a low-energy optical conductivity feature owing to a silicene-based interfacing to the substrate. © 2018 American Chemical Society.

The accurate calculation of electronic excited states of large and electronically correlated biological chromophores in their complex protein environment still represents a challenge for quantum chemistry. Two ab initio techniques are recently emerging as candidates to correctly tackle this issue: Quantum Monte Carlo (QMC) calculations for the ground state geometry optimization, and Many Body Green's Function Theory (MBGFT) for exited state energies. In the present work we use the Variational Monte Carlo (VMC) to carry out structural optimizations and we present an extension of MBGFT to complex environments, using a Quantum Mechanics/Molecular Mechanics framework. This technique is applied to evaluate the optical properties of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin, the protein responsible for dim light vision in the vertebrates. Vertical energies for the bright excitation of RPSB calculated solving the Bethe-Salpeter equation in gas phase and in the protein environment correspond to 2.19 eV and 2.58 eV, respectively. These data are in fair agreement with the available experimental findings. The comparison between these excitation energies and that obtained for a gas phase calculation on a retinal geometry obtained in the protein environment (2.03 eV) reveals the essential role of the protein field in the spectral tuning of the molecule. The proposed VMC/MBGFT methodologies can therefore be applied to obtain a reliable ab initio evaluation of optical properties of biological chromophores. © 2014 Elsevier B.V. All rights reserved.

Colloidal nanocrystals electronic energy levels are determined by strong size-dependent quantum confinement. Understanding the configuration of the energy levels of nanocrystal superlattices is vital in order to use them in heterostructures with other materials. A powerful method is reported to determine the energy levels of PbS nanocrystal assemblies by combining the utilization of electric-double-layer-gated transistors and advanced ab-initio theory.

The relative energy stability between Si(111)2 × 1 positive and negative buckling is still a puzzle. Both isomers possess comparable energies in Density Functional Theory (DFT) calculations and, hence, should occur with the same probability. This is in contrast to experimental findings, which show that the positive buckling is the observed structure at low and room temperature. Here we investigate the role of the exchange-correlation (xc) approximation in DFT functionals. We find that the particular choice of the xc functional does not change the relative stability between the Si(111)2 × 1 isomers. Moreover, we investigate the effect of donor atoms on ground-state and optical properties of both isomers, highlighting the differences with respect to the undoped case for several possible positions of the phosphorus (P) donor atoms. Considering the most stable position of P, relative stability between the isomers is not strongly affected by doping whereas geometric parameters are different with respect to the no doping case. The optical response bears some resemblance with the undoped case but the intensity of reflectance anisotropy peak is decreased for both isomers. © 2013 Elsevier B.V.

We study the electronic properties of two-dimensional (2D) group-III nitrides BN, AlN, GaN, InN, and TlN by first-principles approaches. With increasing group-III atomic number, a decrease of the electronic gap from 6.7 eV to 0 eV takes place. 2D GaN and 2D InN in honeycomb geometry present a direct gap at Γ, while the honeycomb structures of BN and AlN tend to be indirect semiconductors with the valence band maximum at K. Alloying of the nitrides allows tuning the gap with cation composition. Interestingly, Inx Ga1-xN and Inx Tl1-xN alloys enable, with varying x, to construct type I or type II heterostructures. We demonstrate that it is possible to tailor the electronic and optical response from UV to IR. We suggest that 2D InGaN and InTlN heterostructures may efficiently harvest light and serve as building blocks for a future generation of III-V solar cells. Finally, 2D InTlN with a low In content is eligible as the emitter and detector for THz applications.

Transition metal monopnictides represent a new class of topological semimetals with low-energy excitations, namely, Weyl fermions. We report optical properties across a wide spectral energy range for TaAs, TaP, NbAs and NbP, calculated within density functional theory. Spectra are found to be somewhat independent of the anion and the light polarization. Their features are explained in terms of the upper $s$, $p$, $d$, and $f$ electrons. Characteristic absorption features are related to the frequency dependence of the Fresnel reflectivity. While the lower part of the energy loss spectra is dominated by plasmonic features, the high-energy structures are explained by interband transitions., Comment: Added reference 21 to "S.-Y. Xu, et al, Science 349, 613 (2015)"

We present an ab initio investigation of the optical properties of 3-tert-butylcyclohexene in both its conformers. The optical spectra, here the photoabsorption cross section, have been obtained within density-functional theory at the independent-particle level, and within time-dependent density-functional theory. The optical spectra of the two conformers show small but visible differences, hence suggesting that optical absorption experiments can discriminate among the two molecular geometries. To cite this article: K. Gaal-Nagy et al., C. R. Physique 10 (2009).

In this work, we present the results of ab-initio theoretical calculations concerning the electronic and optical properties of Si(001) surface covered by small hydrocarbon molecules, namely acetylene and ethylene. As a result of the adsorption process, both molecules are covalently bonded to the surface, and we point out analogies and differences of the two systems under study. The most stable configurations have been taken into account at different coverages. We will show how band structure and reflectance anisotropy spectra calculations supply additional indirect information concerning the adsorption geometry and the saturation coverage, that have been longly debated.

We review the theoretical framework of ab-initio excited state properties calculations showing the application of these methods to systems of different dimensionality. Many body perturbation theory within the GW approximation of the self energy for the calculation of electronic band structures is presented and applied to liquid water. The Bethe Salpeter equation for the computation of optical properties is illustrated and used for the case of surfaces and liquid water. An alternativemethod for the calculation of optical properties, the Time Dependent Density Functional Theory, is also briefly illustrated. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

The ab initio calculation of optical spectra of sheet crystals usually arranges them in a three-dimensional superlattice with a sufficiently large interlayer distance. We show how the resulting frequency-dependent dielectric tensor is related to the anisotropic optical conductivity of an individual sheet or to the dielectric tensor of a corresponding film with thickness $d$. Their out-of-plane component is taken into account, in contrast to usual treatments. We demonstrate that the generalized transfer-matrix method to model the optical properties of a layer system containing a sheet crystal accounts for all tensor components. As long as $d\ensuremath{\ll}\ensuremath{\lambda}$ ($\ensuremath{\lambda}$-wavelength of light) this generalized formulation of the optical properties for anisotropic two-dimensional (2D) systems of arbitrary thickness reproduces the limits found in literature that are based either on electromagnetic boundary conditions for a conducting surface or on an isotropic dielectric tensor. For $s$-polarized light, the results are independent of the sheet description. For oblique incidence of $p$-polarized light, the tensor nature of the optical conductivity (or the dielectric function) of the sheet crystal strongly impacts on reflectance, transmittance, and absorbance due to the out-of-plane optical conductivity. The limit $d\ensuremath{\rightarrow}0$ should be taken in the final expressions. Example spectra are given for the group-IV honeycomb 2D crystals graphene and silicene.

The absorption and, for the first time, the emission spectra of doped silicon nanocrystals have been calculated within a first-principles framework including geometry optimization. Starting from hydrogenated silicon nanocrystals, simultaneous n- and p-type doping with boron and phosphorous impurities have been considered. We found that the B-P co-doping results to be easier than simple 13- or P-doping and that the two impurities tend to occupy nearest neighbours sites inside the nanocrystal itself. The co-doped nanocrystals bandstructure presents band edge states that are localized on the impurities and are responsible of the red-shifted absorption threshold with respect to that of pure un-doped nanocrystals in fair agreement with the experimental outcorne. The emission spectra show a Stokes shift with respect to the absorption due to the structural relaxation after the creation of the electron-hole pair. Moreover, the absorption and emission spectra have been calculated for a small co-doped nanocrystal beyond the single particle approach by introducing the self-energy correction and solving the Bethe-Salpeter equation scheme. Our procedure shows the important role played by the many-body effects. (C) 2006 Elsevier B.V. All rights reserved.

The proton disorder in ice has a key role in several properties such as the growth mode, thermodynamical properties, and ferroelectricity. While structural phase transitions from proton disordered to proton ordered ices have been extensively studied, much less is known about their electronic and optical properties. Here, we present ab initio many body perturbation theory-based calculations of the electronic and optical properties of cubic ice at different levels of proton disorder. We compare our results with those from liquid water, that acts as an example of a fully (proton- and oxygen-)disordered system. We find that by increasing the proton disorder, a shrinking of the electronic gap occurs in ice, and it is smallest in the liquid water. Simultaneously, the excitonic binding energy decreases, so that the final optical gaps result to be almost independent on the degree of proton disorder. We explain these findings as an interplay between the local dipolar disorder and the electronic correlation.

We present an ab initio study of two semiconductor surfaces, the alpha phase of Sn on Ge(111) and the cleavage surface of diamond. The theoretical tools used (density functional theory (DFT) and many-body perturbation theory) are discussed in detail, and the advantages and disadvantages of the two approaches are pointed out. We show that in the case of diamond it is essential to go beyond the DFT single-particle approach, and to introduce quasiparticle effects through the GW approximation.

In this paper we review the first-principles theoretical framework of the Bethe–Salpeter equation which is nowadays the state-of-the-art approach for including self-energy, local fields and excitonic effects in the surface optical response. Two different approaches for calculating the dielectric screening will be described. In both cases a parallel and efficient iterative algorithm to find numerically the solution of the BSE equation has been implemented. In fact, if the surface states are not energetically separated from the bulk states and if one is interested in describing a large energy window, the traditional approach involving a full diagonalization of a very large excitonic Hamiltonian is prohibitive. The reflectance anisotropy spectrum of the monohydride Si(100) is considered and compared with experiments. A comparison of the results obtained within different treatments of the electron–hole screening is made. Convergence and numerical problems are discussed.

Paper is an important material for many applications. During the centuries, it has been the most widely used writing support and therefore paper degradation is a major issue for cultural heritage. The main component of paper is cellulose, one of the most abundant biomaterials on Earth. Cellulose oxidation is mainly responsible for the yellowing of the ancient samples, through the formation of chromophores. In order to investigate this issue and the chromophores' role, we exploit the optical properties combining non-destructive experiments and theoretical calculations based on ab-initio techniques. In this paper, we illustrate the method and show its application to three ancient paper samples. The procedure we describe is a precious tool for cultural heritage preservation: indeed, the approach we present is based on non-invasive and non-destructive measurements that allows a microscopic understanding of cellulose-based artifacts degradation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In this paper, we present a new noninvasive and nondestructive approach to recover scattering and absorption coefficients from reflectance measurements of highly absorbing and optically inhomogeneous media. Our approach is based on the Yang and Miklavcic theoretical model of light propagation through turbid media, which is a generalization of the Kubelka-Munk theory, extended to accommodate optically thick samples. We show its applications to paper, a material primarily composed of a web of fibers of cellulose, whose optical properties are strongly governed by light scattering effects. Samples studied were ancient and industrial paper sheets, aged in different conditions and highly absorbing in the ultraviolet region. The recovered experimental absorptions of cellulose fibers have been compared to theoretical ab initio quantum-mechanical computational simulations carried out within time-dependent density functional theory. In this way, for each sample, we evaluate the absolute concentration of different kinds of oxidized groups formed upon aging and acting as chromophores causing paper discoloration. We found that the relative concentration of different chromophores in cellulose fibers depends on the aging temperature endured by samples. This clearly indicates that the oxidation of cellulose follows temperature-dependent reaction pathways. Our approach has a wide range of applications for cellulose-based materials, like paper, textiles, and other manufactured products of great industrial and cultural interest, and can potentially be extended to other strongly absorbing inhomogeneous materials. © 2014 American Physical Society.

The dependence of the InP(001) surface reconstruction on the chemical potentials of its constituents is explored. Based on first-principles pseudopotential plane-wave calculations the surface phase diagram is constructed. 17 structural models are studied for the phosphorus-rich InP(001) surfaces, with (2×1), p(2×2) and c(2×2) translational symmetry. P-top dimer reconstructions are favoured. Under less P-rich preparation conditions a tendency for disorder is predicted. STM images are also calculated in order to contribute to a solution of the structural puzzle.

We present ab initio calculations for both the wave functions and the energies of single quasiparticles. The conventional quasiparticle approach evaluates energy-level corrections to first order in the difference between the self-energy and the Kohn-Sham exchange-correlation potential. Here, we also recalculate the quasiparticle states. At the example of the GaAs(110) surface we show that this nonperturbative treatment is important for surfaces with electronic states close in energy but different with respect to their localization. As a sensitive observable the reflectance anisotropy is studied.

We present a first-principles calculation of self-energy effects on the optical properties of the GaAs(110) surface. Three main results are obtained. (a) The self-energy shifts for the valence bands are larger for surface-localized states, at odds with the commonly assumed ``scissor operator'' hypothesis. (b) The computed shifts display an almost linear dependence on the surface localization of the wave function; this allows us to realize a well-converged calculation of optical properties based on the $\mathrm{GW}$-corrected spectrum. (c) The agreement with experimental data is improved with respect to local-density-approximation calculations.

We apply the method of random matrices to a calculation of the optical properties of porous silicon and silicon nanopowders, analyzing the effects of disorder on the visible luminescence properties. The maximum of the luminescence peal; displays a blueshift, which adds up to the effects induced by other mechanisms, such as quantum confinement or surface passivation, and agrees with the experimental findings, The long-wavelength luminescence edge, instead, is redshifted by the presence of disorder, thus partially compensating for the gap-opening effect induced by the other mechanisms.

Graphene, a 2D layer of sp2 bonded carbon atoms in honeycomb arrangement, is a recently synthesized material, with exceptional mechanical, electronic, optical and thermal properties. Although theoretically studied since a long time, as it is the building block of graphite (a stacking of graphene layers), it was isolated as single or few layers only in 2004. Today graphene can be produced by several methods that depend on the quality and dimension of the material to be obtained. Applications of graphene are extensive in electronics, photonics, sensing and also in the field of energy generation and storage. Belonging to the same chemical group of carbon, also silicon could be in principle the ingredient of a 2D material similar to graphene, named silicene. It shares with graphene the peculiar optical and electronic properties and could provide a more easy compatibility with the existing silicon-based microelectronics technology. An extremely high thermal conductivity in the range 3000-5000 Wm-1K-1 has been measured for graphene. Only few results exist instead on the thermal properties of silicene. In this work we report ab-initio calculations, based on density functional theory and density functional perturbation theory, that provide the ingredients for the determination of the thermal conductivity and specific heat of graphene, silicene and 2D silicon carbide. Ab-initio calculations solve Schrodinger equation without the need of empirical parameters, only knowing the chemical nature of the system constituents. The use of consolidated approximations employed in density functional theory allows the accurate prediction of several properties of materials.

We review here some of the most reliable and efficient computational theoretical ab initio techniques for the prediction of optical and electronic spectroscopic properties and show some important applications to molecules, surfaces, and solids. We investigate the role of the solvent in the optical absorption spectrum of indole molecule. We study the excited-state properties of a photo-active minimal model molecule for the retinal of rhodopsin, responsible for vision mechanism in animals. We then show a study about spectroscopic properties of Si(1 1 1) surface. Finally we simulate a bulk system: paper, that is mainly made of cellulose, a pseudo-crystalline material representing 40% of annual biomass production in the Earth.

We show that the low-frequency absorbance of undoped graphene, silicene, and germanene has a universal value, only determined by the Sommerfeld fine-structure constant. This result is derived by means of ab initio calculations of the complex dielectric function for optical interband transitions applied to two-dimensional (2D) crystals with honeycomb geometry. The assumption of chiral massless Dirac fermions is not necessary. The low-frequency absorbance does not depend on the group-IV atom, neither on the sheet buckling nor on the orbital hybridization. We explain these findings via an analytical derivation of the relationship between absorbance and fine-structure constant for 2D Bloch electrons. The effect of deviations of the electronic bands from linearity is also discussed. DOI: 10.1103/PhysRevB.87.035438

Nanostructuring of a material leads to enormous effects on its excited state properties. This study, through the application of different state-of-the-art ab initio theoretical tools, investigates the effect of size on the electronic gap of germanium nanocrystals highlighting similarities and differences with respect to equivalent silicon nanostructures. We performed both GW and ?SCF calculations for the determination of their electronic structure. While it is known that ?SCF corrections to the Kohn-Sham gap vanish for extended systems, the two approaches were expected to be equivalent in the limit of small clusters. However, it has been recently found that for hydrogenated Si clusters the ?SCF gaps are systematically smaller than the GW ones, while the opposite is true for Ag clusters. In this work we find that the GW gaps are larger than the ?SCF ones for all the Ge dots, with the exception of the smallest one. Such crossing between the ?SCF and the GW gap values was not expected and has never been observed before. Moreover, also for hydrogenated Si nanocrystals we found a similar behavior. The origin of this crossing might be found in the Rydberg character of the LUMO of the smallest clusters and can also explain the qualitative differences in the comparison between GW and ?SCF found in the previous studies. © 2013 American Chemical Society.

The recently reported synthesis of silicene in the form of nanoribbons on Ag(110) or 2D epitaxial sheets on Ag(111) aroused considerable interest in the scientific community. Both overlayers were reported to display signatures of Dirac fermions with linearly dispersing electronic bands. In this work, we study the electronic structure of these adsorbate systems within density functional theory. We show that the conical features apparent in angle-resolved photoelectron spectroscopy measurements are not due to silicon but to the silver substrate, as an effect of band folding induced by the Si overlayer periodicity.

We present first-principles studies of the optical absorbance of the group IV honeycomb crystals graphene, silicene, germanene, and tinene. We account for many-body effects on the optical properties by using the non-local hybrid functional HSE06. The optical absorption peaks are blueshifted due to quasiparticle corrections, while the influence on the low-frequency absorbance remains unchanged and reduces to a universal value related to the Sommerfeld fine structure constant. At the Dirac points spin-orbit interaction opens fundamental band gaps; parabolic bands with a very small effective mass emerge. Consequently, the low-frequency absorbance is modified with a spin-orbit-induced transparency region and an increase of the absorbance at the fundamental absorption edge.

The relaxation dynamics of unaligned multi-walled carbon nanotubes decorated with metallic nanoparticles have been studied by using transient optical measurements. The fast dynamics due to the short-lived free-charge carriers excited by the pump are not affected by the presence of nanoparticles. Conversely, a second long dynamics, absent in bare carbon nanotubes, appears only in the decorated samples. A combination of experiment and theory allows us to ascribe this long dynamics to relaxation channels involving electronic states localized at the tube-nanoparticle interface.

The structural and electronic properties of SiC-based two-dimensional (2D) crystals are studied by means of density functional theory and many-body perturbation theory. Such properties cannot simply be interpolated between graphene and silicene. The replacement of half of the C atoms by Si atoms opens a large direct electronic gap and destroys the Dirac cones. Hydrogenation further opens the gap and significantly reduces the electron affinity to 0.1 or 1.8 eV in dependence on the carbon or silicon termination of the 2D crystal surface, thus showing a unique direction dependent ionization potential. This suggests the use of 2D-SiC:H as electron or hole filter.

We show by first-principles calculations that, due to depressed screening and enhanced two-dimensional confinement, excitonic resonances with giant oscillator strength appear in hydrogenated Si and Ge layers, which qualitatively and quantitatively differ from those of graphane. Their large exciton binding energies and oscillator strengths make them promising for observation of novel physical effects and application in optoelectronic devices on the nanoscale.

We present ab initio quantum calculation of the optical properties of formamide in vapor phase and in water solution. We employ time dependent density functional theory for the isolated molecule and many-body perturbation theory methods for the system in solution. An average over several molecular dynamics snapshots is performed to take into account the disorder of the liquid. We find that the excited state properties of the gas-phase formamide are strongly modified by the presence of the water solvent: the geometry of the molecule is distorted and the electronic and optical properties are severely modified. The important interaction among the formamide and the water molecules forces us to use fully quantum methods for the calculation of the excited state properties of this system. The excitonic wave function is localized both on the solute and on part of the solvent.

The Si(111)2$\ifmmode\times\else\texttimes\fi{}$1 is among the most investigated surfaces. Nonetheless, several issues are still not understood. Its reconstruction is well explained in terms of the Pandey model with a slight buckling (tilting) of the topmost atoms; two different isomers of the surface, conventionally named positive and negative buckling, exist. Usually, scanning tunneling microscopy (STM) experiments identify the positive buckling isomer as the stable reconstruction at room temperature. However, at low temperatures and for high $n$ doping of the substrate, recent scanning tunneling spectroscopy (STS) measurements found the coexistence of positive and negative buckling on the Si(111)2$\ifmmode\times\else\texttimes\fi{}$1 surface. In this work, state-of-the-art ab initio methods, based on density functional theory and on many-body perturbation theory, have been used to obtain structural, electronic, and optical properties of Si(111)2$\ifmmode\times\else\texttimes\fi{}$1 positive and negative buckling. The theoretical reflectance anisotropy spectra (RAS), with the inclusion of the excitonic effects, can provide a way to deepen the understanding of the coexistence of the isomers.

The Si(111)2×1 is one of the most studied surfaces. Its reconstruction is described by the Pandey model with a buckling of the topmost atoms. With relation to the sign of the buckling, there are two slightly different geometric structures (isomers), conventionally named positive buckling and negative buckling. STM measurements suggest that the positive buckling isomer is the stable configuration at room temperature, but a recent work, involving STS measurements, has shown the coexistence of both the isomers, at very low temperature, for highly n-doped Si(111)2×1 specimens. There is hence the necessity to deepen the study of the negative buckling isomer, almost completely neglected in literature especially for what concerns its optical properties. In this work we have studied the structural, electronic and optical properties of both the isomers of Si(111)2×1 within the Density Functional Theory in the Local Density Approximation. Our results show that the response to light of the two isomers is sizearly different; Reflectance Anisotropy Spectroscopy would be the right experimental tool to investigate the coexistence of the two isomers.

The yellowing of paper on aging causes major aesthetic damages of cultural heritage. It is due to cellulose oxidation, a complex process with many possible products still to be clarified. By comparing ultraviolet-visible reflectance spectra of ancient and artificially aged modern papers with ab initio time- dependent density functional theory calculations, we identify and estimate the abundance of oxidized functional groups acting as chromophores and responsible of paper yellowing. This knowledge can be used to set up strategies and selective chemical treatments preventing paper yellowing.

In this paper, we give an overview of the state of the art in calculations of the electronic band structure and absorption spectra of water. After an introduction to the main theoretical and computational schemes used, we present results for the electronic and optical excitations of water. We focus mainly on liquid water, but spectroscopic properties of ice and vapor phase are also described. The applicability and the accuracy of first-principles methods are discussed, and results are critically presented.

We apply reflection anisotropy spectroscopy (RAS) to high-quality atomically smooth H/C(100) $2\ifmmode\times\else\texttimes\fi{}1$ surfaces. The optical signal of the H/C(100) ${0}^{\ifmmode^\circ\else\textdegree\fi{}}$ flat surface, and of the H/C(100) ${2}^{\ifmmode^\circ\else\textdegree\fi{}}$ and H/C(100) ${4}^{\ifmmode^\circ\else\textdegree\fi{}}$ vicinal surfaces, is investigated in terms of single and double steps. A comparison of experimental and theoretical results obtained from ab initio calculations shows that, in the energy range considered (1--5 eV), the RAS response can be interpreted in terms of single height ${S}_{B}$ and double height ${D}_{A}$ steps.

We investigate the optical properties of flavin mononucleotide (FMN) as chromophore of a bacterial protein. FMN is studied both in the oxidized and anionic state, by combining hybrid quantum mechanics/molecular mechanics (QM/MM) dynamics with time-dependent density functional theory (TDDFT). Our first-principles calculations show that the inclusion of the protein biological environment is crucial to reproduce the experimental optical spectra.

The effect of the local fields on the absorption spectra of silicon nanoclusters (NCs), freestanding or embedded in SiO(2), is investigated in the DFT-RPA framework for different size and amorphization of the samples. We show that local field effects have a great influence on the optical absorption of the NCs. Their effect can be described by two separate contributions, both arising from polarization effects at the NC interface. First, local fields produce a reduction of the absorption that is stronger in the low energy limit. This contribution is a direct consequence of the screening induced by polarization effects on the incoming field. Secondly, local fields cause a blue shift on the main absorption peak that has been explained in terms of perturbation of the absorption resonance conditions. Both contributions do not depend either on the NC diameter nor on its amorphization degree, while showing a high sensitivity to the environment enclosing the NCs.

We investigate the optical properties of the tZt - penta -3,5- dieniminium cation, a simplified model for the protonated Schiff base of 11- cis retinal in rhodopsin, along the isomerization pathway by ab-initio calculations based on Many-Body Perturbation Theory using the GW method and the Bethe–Salpeter equation. Our calculations are carried out on a few significant CASSCF geometrical configurations of the isomerization minimal energy path taken from the literature. Our excitation energies are qualitatively in agreement with previous Quantum Monte Carlo and post-Hartree–Fock calculations. We also employ TDDFT based methods, and investigate the outcome of using different approximations and several exchange–correlation functionals.

The case study of a 32-atoms Si nanocrystallite (NC) embedded in a SiO 2 matrix, both crystalline and amorphous, or free-standing with different conditions of passivation and strain is analyzed through ab-initio approaches. The Si 32 /SiO 2 heterojunction shows a type I band offset highlighting a separation between the NC plus the interface and the matrix around. The consequence of this separation is the possibility to correctly reproduce the low energy electronic and optical properties of the composed system simply by studying the suspended NC plus interface oxygens with the appropriate strain. Moreover through the definition of an optical absorption threshold we found that, beside the quantum confinement trend, the amorphization introduces an additional redshift that increases with increasing NC size, i.e. the gap tends faster to the bulk limit. Finally, the important changes in the calculated DFT-RPA optical spectra upon inclusion of local fields point towards the need of a proper treatment of the optical response of the interface region.

We present ellipsometry data of the dielectric function of wurtzite ZnO in a wide energy range (2.5-32 eV). The ordinary and extraordinary components show a strong anisotropy above 10 eV, a feature for which ZnO deviates from the other II-VI wurtzite compounds. With the aid of ab initio calculations, performed within many-body perturbation theory (MBPT) and within time-dependent density-functional theory (TDDFT), we analyze the origin of the measured optical structures. TDDFT, with the use of a static long-range exchange-correlation kernel, proves to be a cheaper computational tool than MBPT to yield a good description of the whole spectrum. Theoretical results for the zinc-blende phase are also presented.

First-principles calculations within density functional theory and many-body perturbation theory have been carried out in order to investigate the structural, electronic and optical properties of undoped and doped silicon nanostructures. We consider Si nanoclusters co-doped with B and P. We find that the electronic band gap is reduced with respect to that of the undoped crystals, suggesting the possibility of impurity based engineering of electronic and optical properties of Si nanocrystals. Finally, motivated by recent suggestions concerning the chance of exploiting Ge dots for photovoltaic nanodevices, we present calculations of the electronic and optical properties of a Ge35H36 nanocrystal, and compare the results with those for the corresponding Si35H36 nanocrystals and the co-doped Si33BPH36.