When large structural displacements take place between the ground state (GS) and excited state (ES) minima of polyatomic molecules, the choice of a proper set of coordinates can be crucial for a reliable simulation of the vibrationally resolved absorption spectrum. In this work, we study two carotenoids that undergo structural displacements from GS to ES minima of different magnitude, from small displacements for violaxanthin to rather large ones for β-carotene isomers. Their finite-temperature (77 and 300 K) spectra are simulated at the harmonic level, including Duschinsky effect, by time-dependent (TD) and time-independent (TI) approaches, using (TD)DFT computed potential energy surfaces (PES). We adopted two approaches to construct the harmonic PES, the Adiabatic (AH) and Vertical Hessian (VH) models and, for AH, two reference coordinate frames: Cartesian and valence internal coordinates. Our results show that when large displacements take place, Cartesian coordinates dramatically fail to describe curvilinear displacements and to account for the Duschinsky matrix, preventing a realistic simulation of the spectra within the AH model, where the GS and ES PESs are quadratically expanded around their own equilibrium geometry. In contrast, internal coordinates largely amend such deficiencies and deliver reasonable spectral widths. As expected, both coordinate frames give similar results when small displacements occur. The good agreement between VH and experimental line shapes indicates that VH model, in which GS and ES normal modes are both evaluated at the GS equilibrium geometry, is a good alternative to deal with systems exhibiting large displacements. The use of this model can be, however, problematic when imaginary frequencies arise. The extent of the nonorthogonality of the Dushinsky matrix in internal coordinates and its correlation with the magnitude of the displacement of the GS and ES geometries is analyzed in detail.
The growth of Ti thin films by the magnetron sputtering technique at oblique angles and at room temperature is analysed from both experimental and theoretical points of view. Unlike other materials deposited in similar conditions, the nanostructure development of the Ti layers exhibits an anomalous behaviour when varying both the angle of incidence of the deposition flux and the deposition pressure. At low pressures, a sharp transition from compact to isolated, vertically aligned, nanocolumns is obtained when the angle of incidence surpasses a critical threshold. Remarkably, this transition also occurs when solely increasing the deposition pressure under certain conditions. By the characterization of the Ti layers, the realization of fundamental experiments and the use of a simple growth model, we demonstrate that surface mobilization processes associated to a highly directed momentum distribution and the relatively high kinetic energy of sputtered atoms are responsible for this behaviour.
This work reports the synthesis at room temperature of transparent and colored W(x)Si(y)O(z) thin films by magnetron sputtering (MS) from a single cathode. The films were characterized by a large set of techniques including X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry (RBS), Fourier transform infrared (FT-IR), and Raman spectroscopies. Their optical properties were determined by the analysis of the transmission and reflection spectra. It was found that both the relative amount of tungsten in the W-Si MS target and the ratio O(2)/Ar in the plasma gas were critical parameters to control the blue coloration of the films. The long-term stability of the color, attributed to the formation of a high concentration of W(5+) and W(4+) species, has been related with the formation of W-O-Si bond linkages in an amorphous network. At normal geometry (i.e., substrate surface parallel to the target) the films were rather compact, whereas they were very porous and had less tungsten content when deposited in a glancing angle configuration. In this case, they presented outstanding electrochromic properties characterized by a fast response, a high coloration, a complete reversibility after more than one thousand cycles and a relatively very low refractive index in the bleached state.
A new approach is presented to produce amorphous porous silicon coatings (a-pSi) with closed porosity by magnetron sputtering of a silicon target. It is shown how the use of He as the process gas at moderated power (50-150 W RF) promotes the formation of closed nanometric pores during the growth of the silicon films. The use of oblique-angle deposition demonstrates the possibility of aligning and orientating the pores in one direction. The control of the deposition power allows the control of the pore size distribution. The films have been characterized by a variety of techniques, including scanning and transmission electron microscopy, electron energy loss spectroscopy, Rutherford back scattering and x-ray photoelectron spectroscopy, showing the incorporation of He into the films (most probably inside the closed pores) and limited surface oxidation of the silicon coating. The ellipsometry measurements show a significant decrease in the refractive index of porous coatings (n(500 nm) = 3.75) in comparison to dense coatings (n(500 nm) = 4.75). The capability of the method to prepare coatings with a tailored refractive index is therefore demonstrated. The versatility of the methodology is shown in this paper by preparing intrinsic or doped silicon and also depositing (under DC or RF discharge) a-pSi films on a variety of substrates, including flexible materials, with good chemical and mechanical stability. The fabrication of multilayers of silicon films of controlled refractive index in a simple (one-target chamber) deposition methodology is also presented.
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