A. Marco Saitta

First-principles modeling of the infrared spectrum of kaolinite

Abstract The theoretical infrared spectrum of kaolinite [Al2Si2O5(OH)4, triclinic] was computed using ab initio quantum mechanical calculations. Calculations were performed using the Density Functional Theory and the generalized gradient approximation. The low-frequency dielectric tensor of kaolinite was determined as a function of the light frequency using linear response theory. The IR spectrum was then calculated using a model that takes into account the shape and size of kaolinite particles. A remarkable agreement was obtained between theory and experiment, especially on the position of the stretching bands of OH groups. This agreement provides a firm basis for the interpretation of the IR spectrum of kaolinite in terms of structural parameters

Clar’s Theory, π-Electron Distribution, and Geometry of Graphene Nanoribbons

We show that Clars theory of the aromatic sextet is a simple and powerful tool to predict the stability, the pi-electron distribution, the geometry, and the electronic/magnetic structure of graphene nanoribbons with different hydrogen edge terminations. We use density functional theory to obtain the equilibrium atomic positions, simulated scanning tunneling microscopy (STM) images, edge energies, band gaps, and edge-induced strains of graphene ribbons that we analyze in terms of Clar formulas. On the basis of their Clar representation, we propose a classification scheme for graphene ribbons that groups configurations with similar bond length alternations, STM patterns, and Raman spectra. Our simulations show how STM images and Raman spectra can be used to identify the type of edge termination.

Influence of a knot on the strength of a polymer strand.

Many experiments have been done to determine the relative strengths of different knots, and these show that the break in a knotted rope almost invariably occurs at the point just outside the ‘entrance’ to the knot. The influence of knots on the properties of polymers has become of great interest, in part because of their effect on mechanical properties. Knot theory, applied to the topology of macromolecules indicates that the simple trefoil or ‘overhand’ knot is likely to be present in any long polymer strand. Fragments of DNA have been observed to contain such knots in experiments, and computer simulations. Here we use ab initio computational methods to investigate the effect of a trefoil knot on the breaking strength of a polymer strand. We find that the knot weakens the strand significantly, and that, like a knotted rope, it breaks under tension at the entrance to the knot.

Van der Waals effects in ab initio water at ambient and supercritical conditions

Density functional theory (DFT) within the generalized gradient approximation (GGA) is known to poorly reproduce the experimental properties of liquid water. The poor description of the dispersion forces in the exchange correlation functionals is one of the possible causes. Recent studies have demonstrated an improvement in the simulated properties when they are taken into account. We present here a study of the effects on liquid water of the recently proposed semi-empirical correction of Grimme et al. [J. Chem. Phys. 132, 154104 (2010)]. The difference between standard and corrected DFT-GGA simulations is rationalized with a detailed analysis upon modifying an accurate parameterised potential. This allows an estimate of the typical range of dispersion forces in water. We also show that the structure and diffusivity of ambient-like liquid water are sensitive to the fifth neighbor position, thus highlighting the key role played by this neighbor. Our study is extended to water at supercritical conditions, where experimental and theoretical results are much more scarce. We show that the semi-empirical correction by Grimme et al. improves significantly, although somewhat counter-intuitively, both the structural and the dynamical description of supercritical water.

Ab initio study of gap opening and screening effects in gated bilayer graphene

The electronic properties of doped bilayer graphene in presence of bottom and top gates have been studied and characterized by means of density-functional theory (DFT) calculations. Varying independently the bottom and top gates it is possible to control separately the total doping charge on the sample and the average external electric field acting on the bilayer. We show that, at fixed doping level, the band gap at the

Efficient approach to time-dependent density-functional perturbation theory for optical spectroscopy.

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First-principles study of OH-stretching modes in kaolinite, dickite, and nacrite

point in the Brillouin zone depends linearly on the average electric field, whereas the corresponding proportionality coefficient has a nonmonotonic dependence on doping. We find that the DFT-calculated band gap at

Structure and stability of graphene nanoribbons in oxygen, carbon dioxide, water, and ammonia

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Multiple ionic-plasmon resonances in naturally occurring multiwall nanotubes: Infrared spectra of chrysotile asbestos

, for small doping levels, is roughly half of the band gap obtained with standard tight-binding (TB) approach. We show that this discrepancy arises from an underestimate, in the TB model, of the screening of the system to the external electric field. In particular, on the basis of our DFT results we observe that, when bilayer graphene is in presence of an external electric field, both interlayer and intralayer screenings occur. Only the interlayer screening is included in TB calculations, while both screenings are fundamental for the description of the band-gap opening. We finally provide a general scheme to obtain the full band structure of gated bilayer graphene for an arbitrary value of the external electric field and of doping.

Giant nonadiabatic effects in layer metals: raman spectra of intercalated graphite explained.

Using a superoperator formulation of linearized time-dependent density-functional theory, the dynamical polarizability of a system of interacting electrons is represented by a matrix continued fraction whose coefficients can be obtained from the nonsymmetric block-Lanczos method. The resulting algorithm, which is particularly convenient when large basis sets are used, allows for the calculation of the full spectrum of a system with a computational workload only a few times larger than needed for static polarizabilities within time-independent density-functional perturbation theory. The method is demonstrated with calculation of the spectrum of benzene, and prospects for its application to the large-scale calculation of optical spectra are discussed.