Search results for "conica"
showing 10 items of 118 documents
Basic Concepts and Methodology
2016
In this chapter, the main concepts relevant for the theoretical study of elementary photochemical processes are briefly reviewed. The notions of vibronic coupling and conical intersection are first introduced. The main basic tools from the molecular electronic structure theory and their use for the exploration of potential energy surfaces are then presented.
Three-dimensional field distribution in the focal region of low-Fresnel-number axicons.
2006
Three-dimensional intensity and phase distributions generated by microaxicons are evaluated in the low-Fresnel-number regime. Apertured and nonapertured conical wavefronts may generate transverse patterns with notable deviations from the expected nondiffracting Bessel beam. First-order analytical expressions are proposed for the evaluation of the wave field produced by axicons of different Fresnel number in the focal region.
Spiral conical approximations to double reflection Wolter optics
2008
The design of a grazing incidence focusing optic obtained from a spiral approximation to multiple nested cones produces an annular image of a point source. The angular size of the annulus depends mainly on the pitch of the winding and the focal length. For a spiral conical approximation to Wolter optics, the effect is magnified by the double reflection. However, if the two conical spirals are wound one clock-wise and the other counter-clock-wise, then the aberration is partially compensated. We use a ray tracing code to evaluate advantages and disadvantages of this optical design for potential applications of a light weight optics technology based on plastic foils that we are currently inve…
Thin plastic shell x-ray optics: an update
2003
We present new results from a program to develop large area X-ray telescopes that are made from thin plastic shells. We use multi-shell cylindrical lenses in a point-to-point configuration to form full aperture images of the small focal spot in a an X-ray tube on a microchannel plate detector. The image data are analyzed to yield radial profiles and encircled energy curves. The derived parameters can be extrapolated to the case of a telescope that is a conical approximation to Wolter 1 optics. The plastic shells can be coated with suitable mono- or multilayers that allow for a wideband coverage of X-ray energies. Our current program is focused on the development of a large area, hard X-ray …
Computation of conical intersections by using perturbation techniques
2005
Multiconfigurational second-order perturbation theory, both in its single-state multiconfigurational second-order perturbation theory (CASPT2) and multistate (MS-CASPT2) formulations, is used to search for minima on the crossing seams between different potential energy hypersurfaces of electronic states in several molecular systems. The performance of the procedures is tested and discussed, focusing on the problem of the nonorthogonality of the single-state perturbative solutions. In different cases the obtained structures and energy differences are compared with available complete active space self-consistent field and multireference configuration interaction solutions. Calculations on dif…
Short hydrogen bonds enhance non-aromatic protein-related fluorescence
2020
AbstractFluorescence in biological systems is usually associated with the presence of aromatic groups. Here, we show that specific hydrogen bonding networks can significantly affect fluorescence employing a combined experimental and computational approach. In particular, we reveal that the single amino acid L-glutamine, by undergoing a chemical transformation leading to the formation of a short hydrogen bond, displays optical properties that are significantly enhanced compared to L-glutamine itself. Ab initio molecular dynamics simulations highlight that these short hydrogen bonds prevent the appearance of a conical intersection between the excited and the ground states and thereby signific…
Tangential behavior of functions and conical densities of Hausdorff measures.
2005
We construct a $C^1$-function $f\colon [0,1]\to \mathbb{R}$ such that for almost all $x\in(0,1)$, there is $r>0$ for which $f(y)>f(x)+f'(x)(y-x)$ when $y\in(x,x+r)$ and $f(y)< f(x)+f'(x)(y-x)$ when $y\in(x-r,x)$. The existence of such functions is related to a problem concerning conical density properties of Hausdorff measures on $\mathbb{R}^n$. We also discuss the tangential behavior of typical $C^1$-functions, using an improvement of Jarnik's theorem on essential derived numbers
Dynamics of the scenery flow and geometry of measures
2015
We employ the ergodic theoretic machinery of scenery flows to address classical geometric measure theoretic problems on Euclidean spaces. Our main results include a sharp version of the conical density theorem, which we show to be closely linked to rectifiability. Moreover, we show that the dimension theory of measure-theoretical porosity can be reduced back to its set-theoretic version, that Hausdorff and packing dimensions yield the same maximal dimension for porous and even mean porous measures, and that extremal measures exist and can be chosen to satisfy a generalized notion of self-similarity. These are sharp general formulations of phenomena that had been earlier found to hold in a n…
On the Intrinsically Low Quantum Yields of Pyrimidine DNA Photodamages: Evaluating the Reactivity of the Corresponding Minimum Energy Crossing Points
2020
The low quantum yield of photoformation of cyclobutane pyrimidine dimers and pyrimidine-pyrimidone (6-4) adducts in DNA bases is usually associated with the presence of more favorable nonreactive decay paths and with the unlikeliness of exciting the system in a favorable conformation. Here, we prove that the ability of the reactive conical intersection to bring the system either back to the absorbing conformation or to the photoproduct must be considered as a fundamental factor in the low quantum yields of the mentioned photodamage. In support of the proposed model, the one order of magnitude difference in the quantum yield of formation of the cyclobutane thymine dimer with respect to the t…
A Three-State Model for the Photophysics of Adenine
2006
An ab initio theoretical study at the CASPT2 level is reported on minimum energy reaction paths, state minima, transition states, reaction barriers, and conical intersections on the potential energy hypersurfaces of two tautomers of adenine: 9H- and 7H-adenine. The obtained results led to a complete interpretation of the photophysics of adenine and derivatives, both under jet-cooled conditions and in solution, within a three-state model. The ultrafast subpicosecond fluorescence decay measured in adenine is attributed to the low-lying conical intersection (gs/pipi* La)(CI), reached from the initially populated 1(pipi* La) state along a path which is found to be barrierless only in 9H-adenine…