Experimental and ab-initio calculated vcd spectra of the first OH-stretching overtone of (1R)-(-) and (1S)-(+)-endo-borneol

The near infrared (NIR) absorption and NIR-vibrational circular dichroism (NIR-VCD) spectra of dilute solutions of the two enantiomers of endo-borneol have been measured in the first OH-stretching overtone region (1600–1300 nm). By density functional theory (DFT) we calculate mechanical parameters, i.e. the harmonic mechanical frequency and the anharmonicity constant for the OH stretching, and anharmonic electrical parameters; i.e. the dependence on OH-bond length of atomic polar tensors and atomic axial tensors. We evaluate transition integrals for the calculations of rotational and dipole strengths by Morse anharmonic wavefunctions depending on mechanical harmonic frequencies and mechanical anharmonicity parameters that are calculated ab initio. Experimental and calculated spectra compare quite well and this fact allows us to associate differently signed NIR-VCD features with different conformational states of the OH-bond. Absorption features for the fundamental and for the second overtone of the OH stretching are also compared with experiment

NIR-VCD, vibrational circular dichroism in the near-infrared: Experiments, theory and calculations

The first well documented experiments of Near Infrared Vibrational Circular Dichroism (NIR-VCD) were performed around 1975. We review the thirty year history of NIR-VCD, encompassing both instrumental development and theoretical/computational methods that allow interpretation of experimental spectra, harvesting useful structural information therefrom. We hope to stimulate interest in this still scarcely explored spectroscopy of chiral molecule

Harmonic and Anharmonic Features of IR and NIR Absorption and VCD Spectra of Chiral 4-X-[2.2]Paracyclophanes

The vibrational absorption spectra and vibrational circular dichroism (VCD) spectra of both enantiomers of 4-X-[2.2]paracyclophanes (X ) COOCD3, Cl, I) have been recorded for a few regions in the range of 900- 12000 cm-1. The analysis of the VCD spectra for the two IR regions, 900-1600 cm-1 and 2800-3200 cm-1, is conducted by comparing with DFT calculations of the corresponding spectra; the latter region reveals common motifs of vibrational modes for the three molecules for aliphatic CH stretching fundamentals, whereas in the mid-IR region, one is able to identify specific signatures arising from the substituent groups X. In the CH stretching region between 2900 and 2800 cm-1, we identify and interpret a group of three IR VCD bands due to HCH bending overtone transitions in Fermi resonance with CH stretching fundamental transitions. The analysis of the NIR region between 8000 and 9000 cm-1 for X ) COOCD3 reveals important features of the aromatic CH stretching overtones that are of value since the aromatic CH stretching fundamentals are almost silent. The intensifying of such overtones is attributed to electrical anharmonicity terms, which are evaluated here by ab initio methods and compared with literature data

Dipole and rotational strengths for overtone transitions of a C2-symmetry HCCH molecular fragment using Van Vleck perturbation theory

Contact transformation theory up to second order is employed to treat CH-stretching overtone transitions and to calculate dipole and rotational strengths. A general Hamiltonian describing two interacting CH-stretching oscillators is considered, and the Darling–Dennison resonance is appropriately taken into account. The two CH bonds are supposed to be dissymmetrically disposed, so as to represent a chiral HCCH fragment, endowed with C2 symmetry. Analytical expressions of transition moments and dipole and rotational strengths are given in the hypothesis of general electric and magnetic dipole moments with quadratic dependence on coordinates and momenta. Dipole and rotational strengths are then calculated together with frequencies for the fundamental and first three overtone regions in the simplifying hypothesis of the valence optical approach on the coupled-oscillator framework. Simplified analytical expressions thereof in the relevant parameters are presented

Finding Person Relations in Image Data of the Internet Archive

The multimedia content in the World Wide Web is rapidly growing and contains valuable information for many applications in different domains. For this reason, the Internet Archive initiative has been gathering billions of time-versioned web pages since the mid-nineties. However, the huge amount of data is rarely labeled with appropriate metadata and automatic approaches are required to enable semantic search. Normally, the textual content of the Internet Archive is used to extract entities and their possible relations across domains such as politics and entertainment, whereas image and video content is usually neglected. In this paper, we introduce a system for person recognition in image content of web news stored in the Internet Archive. Thus, the system complements entity recognition in text and allows researchers and analysts to track media coverage and relations of persons more precisely. Based on a deep learning face recognition approach, we suggest a system that automatically detects persons of interest and gathers sample material, which is subsequently used to identify them in the image data of the Internet Archive. We evaluate the performance of the face recognition system on an appropriate standard benchmark dataset and demonstrate the feasibility of the approach with two use cases

Basic Human Values and Moral Foundations Theory in ValueNet Ontology

Values, as intended in ethics, determine the shape and validity of moral and social norms, grounding our everyday individual and community behavior on commonsense knowledge. The attempt to untangle human moral and social value-oriented structure of relations requires investigating both the dimension of subjective human perception of the world, and socio-cultural dynamics and multi-agent social interactions. Formalising latent moral content in human interaction is an appealing perspective that would enable a deeper understanding of both social dynamics and individual cognitive and behavioral dimension. To formalize this broad knowledge area, in the context of ValueNet, a modular ontology representing and operationalising moral and social values, we present two modules aiming at representing two main informal theories in literature: (i) the Basic Human Values theory by Shalom Schwartz and (ii) the Moral Foundations Theory by Graham and Haidt. ValueNet is based on reusable Ontology Design Patterns, is aligned to the DOLCE foundational ontology, and is a component of the Framester factual-linguistic knowledge graph

Absorption flattening as one cause of distortion of circular dichroism spectra of Delta-RuPhen(3) . H(2)TPPS complex

To extend the model that explains why and how much absorption flattening (AF) influences circular dichroism (CD) signals, we have investigated the interesting case of exciton CD in the Soret region of a noncovalent complex formed by (DRuPhen3) 21 and the tetraanionic porphyrin H2TPPS. Different concentrations have been studied by using an AF emulator and spectra simulation. The CD spectra of this compound occasionally show distortions in the solution sampling mode with the increase of concentration; the inhomogeneous distribution in the cell volume is due to aggregation and is the source of the AF effect. On the basis of these results, we conclude that AF is an important cause of distortions in CD spectra for D-RuPhen3 H2TPPS complexes and might affect the CD bands of other aggregated systems as wel

Vibrational Excitons in CH-Stretching Fundamental and Overtone Vibrational Circular Dichroism Spectra

A set of vibrational circular dichroism (VCD) spectra in the CH-stretching fundamental region for about twenty compounds belonging to the class of essential oils was empirically analyzed by the use of a sort of vibrational exciton mechanism, involving three centers. Through a general formula applicable to many coupled dipole oscillators, the rotational strengths of the previously identified vibrational excitons are evaluated. The results are then critically reviewed by the use of recent ab initio methodology, as applied to selected molecules of the original set. Further insight is gained by model calculations adding up the contribution of the coupling between electric dipole moments associated with normal mode behavior and that of the polarizability from polarizable groups. The former part is responsible for the excitonic behavior of the VCD spectra. For the same selected molecules we have also investigated whether some excitonic behavior is taking place in the second overtone region, and have concluded that this is not the case

Reification and Truthmaking Patterns

Reification is a standard technique in conceptual modeling, which consists of including in the domain of discourse entities that may otherwise be hidden or implicit. However, deciding what should be rei- fied is not always easy. Recent work on formal ontology offers us a simple answer: put in the domain of discourse those entities that are responsible for the (alleged) truth of our propositions. These are called truthmakers. Re-visiting previous work, we propose in this paper a systematic analysis of truthmaking patterns for properties and relations based on the ontolog- ical nature of their truthmakers. Truthmaking patterns will be presented as generalization of reification patterns, accounting for the fact that, in some cases, we do not reify a property or a relationship directly, but we rather reify its truthmakers