Search results for "Intersection"
showing 10 items of 213 documents
Excited-state non-radiative decay in stilbenoid compounds: An: Ab initio quantum-chemistry study on size and substituent effects
2019
In the framework of optoelectronic luminescent materials, non-radiative decay mechanisms are relevant to interpret efficiency losses. These radiationless processes are herein studied theoretically for a series of stilbenoid derivatives, including distyrylbenzene (DSB) and cyano-substituted distyrylbenzene (DCS) molecules in vacuo. Given the difficulties of excited-state reaction path determinations, a simplified computational strategy is defined based on the exploration of the potential energy surfaces (PES) along the elongation, twisting, and pyramidalization of the vinyl bonds. For such exploration, density functional theory (DFT), time-dependent (TD)DFT, and complete-active-space self-co…
Geometric characterization and simulation of planar layered elastomeric fibrous biomaterials
2015
An important class of biomaterials is composed of layered networks of elastomeric fibers. While there is a growing interest in modeling and simulation of the mechanical response of these biomaterials, a theoretical foundation for such simulations has yet to be firmly established. The present work addresses this issue in two ways. First, using methods of geometric probability we develop theoretical estimates for the linear and areal fiber intersection densities for two-dimensional fibrous networks. These are expressed in terms of the fiber density and orientation distribution function, both of which are relatively easy to measure properties. Secondly, we develop a random walk algorithm for g…
Redesign of the Geometry of Parts Produced from PBT Composite to Improve Their Operational Behavior
2021
Parts produced from PBT-GF30 (70% polybutylene terephthalate +30% fiberglass) are very often used in car construction, due to the properties of this material. The current trend is to make parts with a shape designed to be as complex as possible, to take over many functions in operation. During the research, a part that is a component of the structure of car safety systems, and that must be completely reliable in operation, was analyzed. This piece has a complex shape that involves the intersection of several walls. Thus, the research aimed at establishing the optimal radius of connection between the walls (R), the ratio between the thickness of the intersecting walls (K) and the angle of in…
Editorial: Calculation of Passenger Car Equivalents at Roundabouts
2021
Editorial on the Research Topic: Calculation of Passenger Car Equivalents at Roundabouts About this Research Topic: Calculation of Passenger Car Equivalents (PCEs) for heavy vehicles represents the starting point for the operational analysis of road facilities and other traffic management applications. PCEs are used to consider the presence of heavy vehicles in the traffic stream and are expressed as multiples of the effect of an average passenger car. Moreover, the highly curvilinear nature of the roundabout design, both in urban and rural environment, has significant effects on the paths that heavy vehicles would travel; as a consequence, the interaction between the physical and performan…
The Travel and Tourism Industry
2017
Earlier chapters focused on the intersection of terrorism and tourism, but this depends on how terrorists changed their tactics to instill terror in society. Some decades ago, terrorists selected celebrities, important persons, or chief police officers as main target of their attacks, but now this role is filled by tourists and global travellers. The situation worsened when Abu Bakr Al-Baghdadi declared jihad against ‘tourism and modern hot-spots of consumption’. The concept of mobilities was historically manipulated by Western powers to impose a one-way discourse which aims to discipline the Other as inferior to European masters.
Modelling Photoionisation in Isocytosine: Potential Formation of Longer‐Lived Excited State Cations in its Keto Form
2021
Abstract Studying the effects of UV and VUV radiation on non‐canonical DNA/RNA nucleobases allows us to compare how they release excess energy following absorption with respect to their canonical counterparts. This has attracted much research attention in recent years because of its likely influence on the origin of our genetic lexicon in prebiotic times. Here we present a CASSCF and XMS‐CASPT2 theoretical study of the photoionisation of non‐canonical pyrimidine nucleobase isocytosine in both its keto and enol tautomeric forms. We analyse their lowest energy cationic excited states including 2π+ , 2nO+ and 2nN+ and compare these to the corresponding electronic states in cytosine. Investigat…
Photoreactivity of Furocoumarins and DNA in PUVA Therapy: Formation of Psoralen−Thymine Adducts
2008
The mechanism of the [2 + 2] cycloaddition photoreaction of psoralen and a DNA nucleobase, thymine, cornerstone of the furocoumarin-based PUVA (psoralen + UVA radiation) phototherapy, has been studied by the quantum-chemical multiconfigurational CASPT2 method. Triplet- and singlet-mediated mono- and diadduct formations have been determined to take place via singlet-triplet crossings and conical intersections, correlated with the initially promoted triplet or singlet states in different possible reactive orientations. Pyroneside monoadducts are suggested to be formed in the triplet manifold of the system, and to be less prone to yield diadducts because of the properties of the monoadduct low…
The Role of Adenine Excimers in the Photophysics of Oligonucleotides
2009
Energies and structures of different arrangements of the stacked adenine homodimer have been computed at the ab initio CASPT2 level of theory in isolation and in an aqueous environment. Adenine dimers are shown to form excimer singlet states with different degrees of stacking and interaction. A model for a 2-fold decay dynamics of adenine oligomers can be supported in which, after initial excitation in the middle UV range, unstacked or slightly stacked pairs of nucleobases will relax by an ultrafast internal conversion to the ground state, localizing the excitation in the monomer and through the corresponding conical intersection with the ground state. On the other hand, long-lifetime intra…
Theoretical Insight into the Spectroscopy and Photochemistry of Isoalloxazine, the Flavin Core Ring
2006
The electronic singlet-singlet and singlet-triplet electronic transitions of the isoalloxazine ring of the flavin core are studied using second-order perturbation theory within the framework of the CASPT2//CASSCF protocol. The main features of the absorption spectrum are computed at 3.09, 4.28, 4.69, 5.00, and 5.37 eV. The lowest singlet (S1) and triplet (T1) excited states are found to be both of pi character with a singlet-triplet splitting of 0.57 eV. On the basis of the analysis of the computed spin-orbit couplings and the potential energy hypersurfaces built for the relevant excited states, the intrinsic mechanism for photoinduced population of T1 is discussed. Upon light absorption, e…
Multiple Decay Mechanisms and 2D-UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine-Uracil Monophosphate
2016
The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D-UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine 1La state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine 1Lb and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter-base hydrogen transfer and decay to the ground state through a conical …