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

Artifacts made of cellulose, such as ancient documents, pose a significant experimental challenge in the THz transmission spectra interpretation due to their small optical thickness. In this Letter we describe a method to recover the complex refractive index of cellulose fibers from the THz transmission data obtained on single freely standing paper sheets in the 0.2-3.5 THz range. By using our technique, we were able to eliminate Fabry-Perot effects and recover the absorption coefficient of the cellulose fibers. The obtained THz absorption spectra are explained in terms of absorption peaks of the cellulose crystalline phase superimposed to a background contribution due to a disordered hydrogen bonds network. The comparison between the experimental spectra with THz vibrational properties simulated by density functional theory calculations confirms this interpretation. In addition, evident changes in the THz absorption spectra are produced by natural and artificial aging on paper samples, whose final stage is characterized by a spectral profile with only two peaks at about 2.1 THz and 3.1 THz. These results could be used to provide a quantitative assessment of the state of preservation of cellulose artifacts.

The discoloration of ancient paper, due to the development of oxidized groups acting as chromophores in its chief component, cellulose, is responsible for severe visual degradation in ancient artifacts. By adopting a non-destructive approach based on the combination of optical reflectance measurements and time-dependent density functional theory ab-initio calculations, we describe and quantify the chromophores affecting Leonardo da Vinci's iconic self-portrait. Their relative concentrations are very similar to those measured in modern and ancient samples aged in humid environments. This analysis quantifies the present level of optical degradation of the Leonardo da Vinci's self-portrait which, compared with future measurements, will assess its degradation rate. This is a fundamental information in order to plan appropriate conservation strategies. (C) 2014 AIP Publishing LLC

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.

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. (C) 2013 Elsevier BAT. All rights reserved