Search results for "conical"
showing 10 items of 109 documents
On Upper Conical Density Results
2010
We report a recent development on the theory of upper conical densities. More precisely, we look at what can be said in this respect for other measures than just the Hausdorff measure. We illustrate the methods involved by proving a result for the packing measure and for a purely unrectifiable doubling measure.
Are the five natural DNA/RNA base monomers a good choice from natural selection?
2009
In order to prevent the damaging effects of sun radiation in the genetic material, its constituent chromophores, the five natural DNA/RNA nucleobases cytosine, thymine, uracil, adenine, and guanine, should be able to efficiently dissipate absorbed radiation, UV specifically, avoiding as much as possible photoreactions leading to lesions. It has been established experimentally and theoretically that efficient internal conversion channels, still open and relevant in the oligomer-stacked strands, exist in the monomers allowing an effective waste of the initial energy. Previous evidences cannot explain, however, why minor differences in the molecular structure modify drastically the photochemis…
Modelling Photoionisations in Tautomeric DNA Nucleobase Derivatives 7H-Adenine and 7H-Guanine: Ultrafast Decay and Photostability
2021
The study of radiation effects in DNA is a multidisciplinary endeavour, connecting the physical, chemical and biological sciences. Despite being mostly filtered by the ozone layer, sunlight radiation is still expected to (photo)ionise DNA in sizeable yields, triggering an electron removal process and the formation of potentially reactive cationic species. In this manuscript, photoionisation decay channels of important DNA tautomeric derivatives, 7H-adenine and 7H-guanine, are characterised with accurate CASSCF/XMS-CASPT2 theoretical methods. These simulation techniques place the onset of ionisation for 7H-adenine and 7H-guanine on average at 8.98 and 8.43 eV, in line with recorded experimen…
Design of the friction stir welding tool using the continuum based FEM model
2006
In friction stir welding (FSW), the welding tool geometry plays a fundamental role in obtaining desirable microstructures in the weld and the heat-affected zones, and consequently improving strength and fatigue resistance of the joint. In this paper, a FSW process with varying pin geometries (cylindrical and conical) and advancing speeds is numerically modeled, and a thermo-mechanically coupled, rigid-viscoplastic, fully 3D FEM analysis able to predict the process variables as well as the material flow pattern and the grain size in the welded joints is performed. The obtained results allow finding optimal tool geometry and advancing speed for improving nugget integrity of aluminum alloys.
A sensitive study of the peculiar jet structure HST-1 in M87
2013
To obtain a better understanding of the location and mechanisms for the production of the gamma-ray emission in jets of AGN we present a detailed study of the HST-1 structure, 0.8 arcsec downstream the jet of M87, previously identified as a possible candidate for TeV emission. HST-1 shows a very peculiar structure with superluminal as well as possible stationary sub-components, and appears to be located in the transition from a parabolic to a conical jet shape, presumably leading to the formation of a recollimation shock. This scenario is supported by our new RHD simulations in which the interaction of a moving component with a recollimation shock leads to the appearance of a new superlumin…
ChemInform Abstract: Excitation of Nucleobases from a Computational Perspective I: Reaction Paths
2016
The main intrinsic photochemical events in nucleobases can be described on theoretical grounds within the realm of non-adiabatic computational photochemistry. From a static standpoint, the photochemical reaction path approach (PRPA), through the computation of the respective minimum energy path (MEP), can be regarded as the most suitable strategy in order to explore the electronically excited isolated nucleobases. Unfortunately, the PRPA does not appear widely in the studies reported in the last decade. The main ultrafast decay observed experimentally for the gas-phase excited nucleobases is related to the computed barrierless MEPs from the bright excited state connecting the initial Franck…
Essential on the Photophysics and Photochemistry of the Indole Chromophore by Using a Totally Unconstrained Theoretical Approach
2015
Indole is a chromophore present in many different molecules of biological interest, such as the essential amino acid tryptophan and the neurotransmitter serotonin. On the basis of CASPT2//CASSCF quantum chemical calculations, the photophysical properties of the system after UV irradiation have been studied through the exploration of the potential energy hypersurfaces of the singlet and triplet low-lying valence excited states. In contrast to previous studies, the present work has been carried out without imposing any restriction to the geometry of the molecule (C1 symmetry) and by performing minimum energy path calculations, which is the only instrument able to provide the lowest-energy evo…
A theoretical study on the thermal ring opening rearrangement of 1H-bicyclo[3.1.0]hexa-3,5-dien-2-one: a case of two state reactivity
2009
The molecular mechanism of the thermal rearrangement of singlet 1H-bicyclo[3.1.0]hexa-3,5-dien-2-one to give triplet 4-oxocyclohexa-2,5-dienylidene has been investigated using density functional theory (B3LYP and M05-2X functionals) as well as ab initio CASSCF and CASPT2 multiconfigurational methods. The reactant has a singlet ground state while the product can be found in three low lying electronic states P((3)B(1)), P((1)B(1)), and P((1)A'). Therefore, the molecular mechanism of this ring opening rearrangement may involve up to three different potential energy surfaces of two spin multiplicities: two singlet (closed shell, CS, and open shell, OS) and one triplet. The stationary points on …
Inverted energy gap law for the nonradiative decay in fluorescent floppy molecules: larger fluorescence quantum yields for smaller energy gaps
2019
A data survey on experimental fluorescence quantum yields of (multi)substituted dicyano-distyrylbenzenes in fluid solution evidences that non-radiative decay increases with the Franck-Condon energy (E-FC), being opposite to the conventional energy gap law. Quantum-chemistry indicates that this is controlled by access to the conical intersection (CI) following the Bell-Evans-Polanyi principle as a first-step approximation for this family of molecules; the variations in E-FC among the different compounds are found to be decisive, while those of E-CI are estimated to be weaker or even enhancing the effect. The current findings may have significant consequences for the design of molecules for o…
A Comprehensive Observational Study of Graupel and Hail Terminal Velocity, Mass Flux, and Kinetic Energy
2018
Abstract This study uses novel approaches to estimate the fall characteristics of hail, covering a size range from about 0.5 to 7 cm, and the drag coefficients of lump and conical graupel. Three-dimensional (3D) volume scans of 60 hailstones of sizes from 2.5 to 6.7 cm were printed in three dimensions using acrylonitrile butadiene styrene (ABS) plastic, and their terminal velocities were measured in the Mainz, Germany, vertical wind tunnel. To simulate lump graupel, 40 of the hailstones were printed with maximum dimensions of about 0.2, 0.3, and 0.5 cm, and their terminal velocities were measured. Conical graupel, whose three dimensions (maximum dimension 0.1–1 cm) were estimated from an an…