Search results for "ROTATION"
showing 10 items of 935 documents
Habilitation Thesis
2004
This habilitation thesis presents a synthesis of my research activities during the last eight years. I have distinguished, one the one hand, researches concerning rovibrational spectroscopy in a singlet electronic state (Part III) and, on the other hand, those concerning rovibronic spectroscopy in a degenerate electronic state (Part IV).
Ultrafast ring-opening/closing and deactivation channels for a model spiropyran-merocyanine system.
2011
The photochemistry of a model merocyanine-spiropyran system was analyzed theoretically at the MS-CASPT2//SA-CASSCF(14,12) level. Several excited singlet states were studied in both the closed spiropyran and open merocyanine forms, and the paths to the different S(1)/S(0) conical intersections found were analyzed. After absorption of UV light from the spiropyran form, there are two possible ultrafast routes to efficient conversion to the ground state; one involves the rupture of the C(spiro)-O bond leading to the open form and the other involves the lengthening of the C(spiro)-N bond with no photoreaction. From the merocyanine side the excited state can reach a very broad S(1)/S(0) conical i…
Supersaturation and activity-rotation relation in PMS stars: the young Cluster h Per
2016
The magnetic activity of late-type MS stars is characterized by different regimes, and their activity levels are well described by Ro, the ratio between P_rot and the convective turnover time. Very young PMS stars show, similarly to MS stars, intense magnetic activity. However they do not show clear activity-rotation trends, and it still debated which stellar parameters determine their magnetic activity levels. To bridge the gap between MS and PMS stars, we studied the activity-rotation relation in the young cluster h Per, a ~13 Myr old cluster, that contains both fast and slow rotators, whose members have ended their accretion phase and have already developed a radiative core. It offers us…
Photometric and spectroscopic variability of the B5IIIe star HD 171219
2017
We analyzed the star HD 171219, one of the relatively bright Be stars observed in the seismo field of the CoRoT satellite, in order to determine its physical and pulsation characteristics. Classical Be stars are main-sequence objects of mainly B-type, whose spectra show, or have shown at some epoch, Balmer lines in emission and an infrared excess. Both characteristics are attributed to an equatorially concentrated circumstellar disk fed by non-periodic mass-loss episodes (outbursts). Be stars often show nonradial pulsation gravity modes and, as more recently discovered, stochastically excited oscillations. Applying the CLEANEST algorithm to the high-cadence and highly photometrically precis…
Unusual interaction extended between the pyranose ring oxygen and Zn(II) center in the complexes derived from 4,6-O-butylidene/ethylidene-N-(α-hydrox…
2003
The Zn(II) complexes of 4,6-O-butylidene/ethylidene-N-(α-hydroxynaphthylidene/o-hydroxybenzylidene)-β-Image -glucopyranosylamine have been synthesized and characterized using spectral and analytical methods and structure for one of the products was established. The geometry of the complexes vary from unusual distorted trigonal bipyramidal to pseudo-bicapped tetrahedron depending upon the extent of binding of pyranose ring oxygens to the Zn(II) ion, as evidenced from crystal structures. Such interaction is also reflected on the optical rotation and CD spectral properties of these complexes in solution.
Structural studies of acyl esters of entacapone
2001
Abstract The crystal structures of entacapone [(E)-2-cyano-N,N-diethyl-3-(3,4-dihydroxy-5-nitrophenyl)propenamide] and three of its acyl esters were solved. Entacapone, and its monopivaloate and diacetate derivatives, exist in the E-form while its dibenzoate derivative adopts the Z-form in the crystalline state. The ethyl substituents of the E-form are not freely rotating, as demonstrated by the broad signals in the 1H and 13C NMR spectra. The rotation barrier for the E-form was defined by the crystal structures, which show that free rotation of the ethyl substituents is blocked by the cyano-group.
Dual Substituent Parameter Modeling of Theoretical, NMR and IR Spectral Data of 5-Substituted Indole-2,3-diones
2002
Correlations of AM1 and PM3 theoretical data, 13C-NMR substituent chemical shifts (13C-SCS) and IR carbonyl group wave numbers [ν(C3â•ÂO)] were studied using dual substituent parameter (DSP) models for 5-substituted indole-2,3-diones. For the C7 atom a reverse substituent effect attributed to extended À-polarization was observed. On the other hand, the DSP approaches for the C3 atom showed normal substituent effects with some contribution of reverse effect supported strongly by 13C-SCS correlations. In the ν(C3â•ÂO) and p(C3â•ÂO) DSP correlations the field effect contribution predominates over the resonance effect, which justifies the using of earlier suggested vibrational cou…
Barriers to rotation in ortho-substituted tertiary aromatic amides: Effect of chloro-substitution on resonance and distortion
2018
Planarity of the amide bond represents one of the most widely recognized properties of amides. Herein, we report a combined structural and computational study on the effect of ortho-substitution on resonance and barriers to rotation in tertiary aromatic amides. We demonstrate that ortho-chloro substitution in a class of benzamides that are important from the reactivity and medicinal chemistry perspective results in increased barriers to rotation around both the N-C(O) and C-C(O) axes. The effect of steric hindrance on structures, resonance energies, barriers to rotation, and proton affinities is discussed. The present study strongly supports the use of ortho-substitution in common benzamide…
Pyrrolidine in Drug Discovery: A Versatile Scaffold for Novel Biologically Active Compounds
2021
AbstractThe five-membered pyrrolidine ring is one of the nitrogen heterocycles used widely by medicinal chemists to obtain compounds for the treatment of human diseases. The great interest in this saturated scaffold is enhanced by (1) the possibility to efficiently explore the pharmacophore space due to sp3-hybridization, (2) the contribution to the stereochemistry of the molecule, (3) and the increased three-dimensional (3D) coverage due to the non-planarity of the ring—a phenomenon called “pseudorotation”. In this review, we report bioactive molecules with target selectivity characterized by the pyrrolidine ring and its derivatives, including pyrrolizines, pyrrolidine-2-one, pyrrolidine-2…
Structure finding in cosmological simulations: the state of affairs
2013
The ever increasing size and complexity of data coming from simulations of cosmic structure formation demands equally sophisticated tools for their analysis. During the past decade, the art of object finding in these simulations has hence developed into an important discipline itself. A multitude of codes based upon a huge variety of methods and techniques have been spawned yet the question remained as to whether or not they will provide the same (physical) information about the structures of interest. Here we summarize and extent previous work of the "halo finder comparison project": we investigate in detail the (possible) origin of any deviations across finders. To this extent we decipher…