Search results for "Clusters"

Induced Chirality in Confined Space on Halogen Gold Complexes

2015

The solubilization of HAuCl4 in toluene within optically active reverse micelles and lamellar structures formed by (1R,2S)-Dodecyl(2-hydroxy-1-methyl-2-phenylethyl)- dimethylammonium bromide (DMEB) has allowed us to evidence the complex phenomenology accompanying the confinement of Au salt within these nanostructures. Together with a chloride/bromide exchange process occurring in the first coordination sphere of an Au ion, UV−vis and electronic circular dichroism (ECD) spectra reveal the appearance of an induced dichroic signal attributable to Au complexes entrapped in the hydrophilic domain of the DMEB chiral nanostructures. Interestingly, change of the effective oxidation state and coordi…

From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters

2018

A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13 Cu2 , into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13 Cu2 (DPPP)3 (SPy)6 ]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13 Cu2 ((2r,4r)/(2s,4s)-BDPP)3 (SPy)6 ]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images in the range of 250-500 nm with maximum anisotropy factors of 1.2×10-3 . DFT calculations provided good corre…

Real-Time Observation of “Soft” Magic-Size Clusters during Hydrolysis of the Model Metallodrug Bismuth Disalicylate

2021

International audience; Colloidal bismuth therapeutics have been used for hundreds of years, yet remain mysterious. Here we report an X-ray pair distribution function (PDF) study of the solvolysis of bismuth disalicylate, a model for the metallodrug bismuth subsalicylate (Pepto-Bismol). This reveals catalysis by traces of water, followed by multistep cluster growth. The ratio of the two major species, {Bi9O7} and {Bi38O44}, depends on exposure to air, time, and the solvent. The solution-phase cluster structures are of significantly higher symmetry in comparison to solid-state analogues, with reduced off-center Bi3+ displacements. This explains why such “magic-size” clusters can be both stab…

SMART: Unique splitting-while-merging framework for gene clustering

2014

© 2014 Fa et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. Successful clustering algorithms are highly dependent on parameter settings. The clustering performance degrades significantly unless parameters are properly set, and yet, it is difficult to set these parameters a priori. To address this issue, in this paper, we propose a unique splitting-while-merging clustering framework, named "splitting merging awareness tactics" (SMART), which does not require any a priori knowledge of either the number …

Advanced Indexing Schema for Imaging Applications: Three-Case Studies

2007

Bayesian versus data driven model selection for microarray data

2014

Clustering is one of the most well known activities in scientific investigation and the object of research in many disciplines, ranging from Statistics to Computer Science. In this beautiful area, one of the most difficult challenges is a particular instance of the model selection problem, i.e., the identification of the correct number of clusters in a dataset. In what follows, for ease of reference, we refer to that instance still as model selection. It is an important part of any statistical analysis. The techniques used for solving it are mainly either Bayesian or data-driven, and are both based on internal knowledge. That is, they use information obtained by processing the input data. A…

Ultrafast dynamics of halogens in rare gas solids

2007

We perform time resolved pump-probe spectroscopy on small halogen molecules ClF, Cl2, Br2, and I2 embedded in rare gas solids (RGS). We find that dissociation, angular depolarization, and the decoherence of the molecule is strongly influenced by the cage structure. The well ordered crystalline environment facilitates the modelling of the experimental angular distribution of the molecular axis after the collision with the rare gas cage. The observation of many subsequent vibrational wave packet oscillations allows the construction of anharmonic potentials and indicate a long vibrational coherence time. We control the vibrational wave packet revivals, thereby gaining information about the vib…

Mass-asymmetric fission in the 40ca+142Nd reaction

2016

Shell effects play a major role in fission. Mass-asymmetric fission observed in the spontaneous and low energy fission of actinide nuclei was explained by incorporating the fragment shell properties in liquid drop model. Asymmetric fission has also been observed in the low energy fission of neutron-deficient 180 Hg nuclei in recent β -delayed fission experiments. This low-energy β -delayed fission has been explained in terms of strong shell effects in pre-scission configurations associated with the system after capture. Calculations predicted asymmetric fission for heavier Hg isotopes as well, at compound nuclear excitation energy as high as 40 MeV. To explore the evolution of fission fragm…

Multicollision-induced dissociation of multiply charged gold clusters, Aun2+, n = 7–35, and Aun3+, n = 19–35

2000

Abstract Multicollision-induced dissociation (MCID) has been applied to gold clusters, Au n 2+ (n = 7–35) and Au n 3+ (n = 19–35) stored in a Penning trap. By application of ion cyclotron resonance excitation and pulses of argon collision gas, fragmentation yields have been measured as a function of the clusters’ kinetic energy. The corresponding dissociation energies have been determined by use of the impulsive collision theory and the quantum Rice–Ramsperger–Kassel (RRK) model for the energy transfer to internal cluster modes and for delayed dissociation, respectively. As compared to earlier measurements of singly charged gold clusters the variation of the stability as a function of clust…

A Theoretical Determination of the Low-lying Electronic States of the p-Benzosemiquinone Radical Anion

2000

The low-lying electronic states of the p-benzosemiquinone radical anion are studied using multiconfigurational second-order perturbation theory (CASPT2) and extended atomic natural orbital (ANO) ba...