Break-up stage restoration in multifragmentation reactions

In the case of Xe + Sn at 32MeV/nucleon multifragmentation reaction break-up fragments are built up from the experimentally detected ones using evaluations of light-particle evaporation multiplicities which thus settle fragment internal excitation. Freeze-out characteristics are extracted from experimental kinetic energy spectra under the assumption of full decoupling between fragment formation and energy dissipated in different degrees of freedom. The thermal kinetic energy is determined uniquely while for the freeze-out volume - collective energy a multiple solution is obtained. The coherence between the solutions of the break-up restoration algorithm and the predictions of a multifragmentation model with identical definition of primary fragments is regarded as a way to select the true value. The broad kinetic energy spectrum of ³He is consistent with the break-up genesis of this isotope.     

Convergence to extremal processes in random environments and extremal ageing in SK models

This paper extends recent results on ageing in mean field spin glasses on short time scales, obtained by Ben Arous and Gün (Commun Pure Appl Math 65:77–127, 2012) in law with respect to the environment, to results that hold almost surely, respectively in probability, with respect to the environment. It is based on the methods put forward in (Gayrard in Aging in reversible dynamics of disordered systems. II. Emergence of the arcsine law in the random hopping time dynamics of the REM, 2010; Electron J Probab 17(58): 1–33, 2012) and naturally complements (Bovier and Gayrard in Ann Probab, 2012).     

Gain narrowing in few-atom systems

Using a density matrix approach, we study the simplest systems that display both gain and feedback: clusters of 2 to 5 atoms, one of which is pumped. The other atoms supply feedback through multiple scattering of light. We show that, if the atoms are in each other's near field, the system exhibits large gain narrowing and spectral mode redistribution. The observed phenomena are more pronounced if the feedback is enhanced. Our system is to our knowledge the simplest exactly solvable microscopic system which shows the approach to laser oscillation.     

Excited-state proton transfer in 7-hydroxy-4-methylcoumarin along a hydrogen-bonded water wire

TDDFT, RI-CC2, and CIS calculations have been performed for the nondissociative excited-state proton transfer (ESPT) in the S1 state of 7-hydroxy-4-methylcoumarin (7H4MC) along a H-bonded water wire of three water molecules bridging the proton donor (OH) and the proton acceptor (C[double bond]O) groups (7H4MC.(H2O)3). The observed structural reorganization in the water-wire cluster is interpreted as a proton-transfer (PT) reaction along the H2O solvent wire. The shift of electron density within the organic chromophore 7H4MC due to the optical excitation appears to be the driving force for ESPT. All the methods used show that the reaction path occurs in the 1pipi* state, and no crossing with a Rydberg-type 1pisigma* state is found. TDDFT and RI-CC2 calculations predict an exoergic reaction of the excited-state enol-to-keto transformation. The S1 potential energy curve reveals well-defined Cs minima of enol- and keto-clusters, separated by a single barrier with a height of 17-20 kcal/mol. After surmounting this barrier, spontaneous PT along the water wire is observed, leading without any further barrier to the keto structure. The TDDFT and RI-CC2 methods appear to be reliable approaches to describe the energy surfaces of ESPT. The CIS method predicts an endoergic ESPT reaction and an energy barrier, which is too high.     

The charge-transfer states in a stacked nucleobase dimer complex: a benchmark study

Electronic singlet excitations of stacked adenine-thymine (AT) and guanine-cytosine (GC) complexes have been investigated with respect to local excitation and charge-transfer (CT) characters. Potential energy curves for rigid displacement of the nucleobases have been computed to establish the distance dependence of the CT states. The second-order algebraic diagrammatic construction [ADC(2)] method served as reference approach for comparison to a selected set of density functionals used within the time-dependent density functional theory (TD-DFT). Particular attention was dedicated to the performance of the recently developed family of M06 functionals. The calculations for the stacked complexes show that at the ADC(2) level, the lowest CT state is S(6) for the AT and as S(4) for the GC pair. At the reference geometry, the actual charge transferred is found to be 0.73 e for AT. In case of GC, this amount is much smaller (0.17 e). With increasing separation of the two nucleobases, the CT state is strongly destabilized. The M06-2X version provides a relatively good reproduction of the ADC(2) results. It avoids the serious overstabilization and overcrowding of the spectrum found with the B3LYP functional. On the other hand, M06-HF destabilizes the CT state too strongly. TD-DFT/M06-2X calculations in solution (heptane, isoquinoline, and water) using the polarizable continuum model show a stabilization of the CT state and an increase in CT character with increasing polarity of the solvent.     

Control of light transmission through opaque scattering media in space and time

We report the first experimental demonstration of combined spatial and temporal control of light transmission through opaque media. This control is achieved by solely manipulating spatial degrees of freedom of the incident wave front. As an application, we demonstrate that the present approach is capable of forming bandwidth-limited ultrashort pulses from the otherwise randomly transmitted light with a controllable interaction time of the pulses with the medium. Our approach provides a new tool for fundamental studies of light propagation in complex media and has the potential for applications for coherent control, sensing and imaging in nano- and biophotonics.     

Determination of Heavy Metals in Bio-Collectors as Indicator of Environmental Pollution

The heavy metal levels in bio-collector ( Fabaceae Rabinia Pseudoacacia L. sprouts) samples collected from seven sites, which had the characteristic properties of the Sivas city, Turkey, in year 2000, have been determined by atomic absorption spectrometry (AAS), after the bio-collector sprouts were prepared for analysis by bio-collector-ultrasonic leaching method (BC-ULM). The results of the analyses were used to determine major sources and magnitude of heavy metal pollution. The mean concentration levels of Pb, Cu, Ni, Zn and Cd were found to be 6.8, 5.5, 6.7, 12.4 and 0.20 µg/g fresh bio-collector, respectively, for September 2000. The highest levels of the heavy metals at the sites affected by industrial emissions and heavy traffic were noted. The heavy metal levels in urban bio-collectors were several times higher than the background levels. After heavy metal pollution factors of each site were determined, their possible major pollutant sources were discussed.     

Enthalpy and Entropy Barriers Explain the Effects of Topology on the Kinetics of Zeolite‐Catalyzed Reactions

The methylation of ethene, propene, and trans‐2‐butene on zeolites H‐ZSM‐58 (DDR), H‐ZSM‐22 (TON), and H‐ZSM‐5 (MFI) is studied to elucidate the particular influence of topology on the kinetics of zeolite‐catalyzed reactions. H‐ZSM‐58 and H‐ZSM‐22 are found to display overall lower methylation rates compared to H‐ZSM‐5 and also different trends in methylation rates with increasing alkene size. These variations may be rationalized based on a decomposition of the free‐energy barriers into enthalpic and entropic contributions, which reveals that the lower methylation rates on H‐ZSM‐58 and H‐ZSM‐22 have virtually opposite reasons. On H‐ZSM‐58, the lower methylation rates are caused by higher enthalpy barriers, owing to inefficient stabilization of the reaction intermediates in the large cage‐like pores. On the other hand, on H‐ZSM‐22, the methylation rates mostly suffer from higher entropy barriers, because excessive entropy losses are incurred inside the narrow‐channel structure. These results show that the kinetics of crucial elementary steps hinge on the balance between proper stabilization of the reaction intermediates inside the zeolite pores and the resulting entropy losses. These fundamental insights into their inner workings are indispensable for ultimately selecting or designing better zeolite catalysts.