The ENEA noble gas laboratory: status of implementation

The strategic value of noble gas capability has been recently recognized by ENEA for the acquisition of data about anthropogenic activities. Within the framework of institutional agreements, a laboratory for measurement of radioactive noble gases is under construction for environmental analysis and for monitoring studies in connection with issues related to the nuclear fuel cycle to distinguish the anthropogenic contributions to the environment. This research is intended to contribute also to the international effort to support the comprehensive nuclear-test-ban treaty verification capability. The present work summarizes the status of implementation of the noble gas laboratory at the ENEA Brasimone research centre that is located in the north-centre part of Italy by the Brasimone lake at about 850 m altitude. The radionuclides of interest are the following four xenon radioisotopes: ^131mXe, ^133mXe, ¹³³Xe and ¹³⁵Xe. The noble gas system under development at ENEA has three separate components: air collection (sampling and adsorption), processing (gas extraction and purification) and measurement (gamma-ray spectrometry analysis). The separation of the sampling equipment from the analysis is seen as necessary for the effectiveness of extensive sampling campaigns, as required in monitoring programs. Refurbishment is currently under way to accommodate a more sensitive acquisition system.     

Light scalars coupled to photons and non-newtonian forces

A particle phi coupling to two photons couples also radiatively to charged particles, like protons. If the particle is a light scalar, this induced coupling leads to spin-independent non-Newtonian forces. We show that the experimental constraints on exotic, fifth-type forces lead to stringent constraints on the phigammagamma coupling. We discuss the impact on the recent PVLAS results and the role of paraphoton models introduced to solve the PVLAS-CAST puzzle.     

Highly excited “nuclear molecules”: A way to explain the fluctuations in DBHIC excitation functions. Study of the28Si +28Si colliding system at 5.3 MeV ·A

The properties of the strong fluctuations observed in the excitation functions of Dissipative Binary Heavy Ion Collisions (DBHIC) have been studied for the system²⁸Si+²⁸Si in the energy range 150 MeV ≤E _lab ≤ 156 MeV with 150 keV step laboratory incident energy, by angular distributions and excitation functions measurements. Experimental results are compared to the the recently developed Partially Overlapping Molecular Level Model (POMLM). The parameters of the model have been determined with reasonable accuracy by describing all the quantities characterizing the fluctuations in the excitation functions i.e.: Average Angular Distributions, Energy Autocorrelation Functions, Variances, Angular Correlation Coefficients. The results of the analysis strongly support the idea of a process proceeding through the formation of an highly excited “nuclear molecule”. Experimental data collected at the most forward angles show the effects of strong excitation of a few final channels.     

Nonlinear modelling and control of a common rail injection system for diesel engines

Modern trends in designing mechatronic systems call for a synergic design of the separated subsystems (mechanic, electronic parts, control modules, etc.) concurring to the overall performance. Following this point of view, this paper presents a control oriented model and a nonlinear control design for a Common Rail injection system. First a model is developed, which is tuned in a virtual simulation environment, representing the injection system in details in a reliable replication of reality. Then a sliding mode control is developed. Both the model of the injection process and of the control law are validated by a virtual detailed simulation environment. The prediction capability of the model and the control efficiency are clearly shown.     

Applicability of medium-size basis sets in calculations of molecular dynamic polarisabilities

Static and dynamic average polarisabilities and polarisability anisotropies of seven linear non-polar and polar molecules are calculated within the CCS, CC2, and CC3 approximations using a range of medium-sized basis sets: the polarised LPol-n (n = ds, dl, fs, fl), the aug-pc-n (n = 1, 2), the def2-SVPD, and -TZVPD basis sets. Reference values are obtained using a hierarchy of Dunning's (d-)aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The results are discussed together with the available CCSD values in terms of basis set and correlation method errors, and their ratio. Detailed analysis shows that already the def2-SVPD basis set can be used in CCS polarisability calculations. When affordable, the slightly larger aug-pc-1 basis set is recommended, as it leads to significant reduction of basis set error. The def2-TZVPD, LPol-ds, and aug-pc-2 basis sets are optimal choice within the CC2 approximation, with the latter allowing to approach the CC2 basis set limit. The LPol-ds, -dl, and def2-TZVPD sets outperform the aug-cc-pVTZ set in average polarisability CCSD calculations, with the def2-TZVPD being competitive to other reduced-size sets also in determination of polarisability anisotropy. The aug-pc-2 basis is a particularly attractive choice for CCSD, giving the accuracy of aug-cc-pVQZ at a significantly reduced computational cost. The polarisability anisotropy is shown to be more computationally demanding than the average polarisability, in particular with respect to the accuracy of the correlation method and an accurate evaluation of this property requires at least the CCSD model.     

Vibronically resolved electronic circular dichroism spectra of (R)-(+)-3-methylcyclopentanone: a theoretical study

The vibrationally resolved electronic circular dichroism (ECD) spectra of the two dominant conformers of (R)-(+)-3-methylcyclopentanone in gas phase are computed by density functional response theory, with a full account of Franck-Condon and Herzberg-Teller vibrational contributions at the harmonic level. Proper inclusion of the latter contributions was made possible by the recent implementation of effective-scaling computations of vibrational overlaps and of analytical gradients of time dependent DFT. The Coulomb-attenuated Becke three parameters Lee-Yang-Parr (CAM-B3LYP) functional reproduces both the position and the intensity of the experimental peaks, providing a remarkable improvement over the spectra obtained with the popular hybrid B3LYP functional, and allowing a confident assignment of the CD fine vibrational structure. Franck-Condon and Herzberg-Teller contributions are discussed in detail. The computed decrease of the CD intensity in the gas phase upon increase of the temperature of the sample follows the trend observed experimentally in different solvents.     

Ab initio study of the one- and two-photon circular dichroism of R-(+)-3-methyl-cyclopentanone

One- and two-photon circular dichroism spectra of R-(+)-3-methyl-cyclopentanone, a system that has been the subject of recent experimental studies of (2+1) resonance-enhanced multiphoton ionization circular dichroism, have been calculated with an origin-invariant density functional theory approximation in the region of the lowest electronic excited states, both for the gas phase and for a selection of solvents. A polarizable continuum model is used in the calculations performed on the solvated system. Two low-lying conformers are analyzed, and a comparison of the intensities and characteristic features is made with the corresponding two-photon absorption for each species, also for the Boltzmann-averaged spectra. The effect of the choice of geometry, basis set, and exchange-correlation functional is carefully analyzed. It is found that a density functional theory approach using the Coulomb attenuating method variant of Becke's three-parameter exchange and the Lee-Yang-Parr correlation functionals with correlation-consistent basis sets of double-zeta quality can reproduce the experimental electronic circular dichroism spectra very well. The features appearing in experiment are characterized in terms of molecular excitations, and the differences in the response of each state in the one- and two-photon processes are highlighted.     

Chemical and electrochemical oxidation of C8-arylamine adducts of 2'-deoxyguanosine

The electrochemical and chemical oxidation of a series of C8-arylamine adducts of 2'-deoxyguanosine has been examined. The oxidations were found to be reversible by cyclic and square-wave voltammetry in both aqueous buffer and aprotic organic solvent. The mechanism of the oxidation in protic media was either one- or two-electron, depending on the aryl group. The chemical oxidation resulted in guanidinohydantoin and spiroiminodihydantoin rearrangement products similar to those observed for 8-oxo-7,8-dihydro-2'-deoxyguanosine.     

Synthesis of chiral β-3-amino-2-hydroxyalkanoates and 3-alkyl-3-hydroxy-β-lactams by double asymmetric induction

Reactions of chiral (2S)-enolates of dioxolan-4-ones, derived from lactic, mandelic, and phenyllactic acids, with aliphatic (S_S)- and (S_R)-tert-butylsulfinyl aldimines afforded conformationally restrained C2-disubstituted N,O-orthogonally protected 3-amino-2-hydroxyalkanoates in the form of N-sulfinyl protected 1′-aminodioxolan-4-ones. The product distribution showed that there is significant kinetic selectivity, due to the presence of ‘matched’ and ‘mismatched’ components, between the (S)- or (R)-tert-butylsulfinyl aldimines and the (2S)-enolates of the 1,3-dioxolan-4-ones. Selective methoxide-induced removal of the acetal group of the N-sulfinyl-1′-aminodioxolanones yielded the corresponding N-sulfinyl protected methyl alkanoates. In addition, the selective acid-induced removal of the sulfinyl group of the N-sulfinyl-1′-aminodioxolanones provided the corresponding N-unprotected 1′-aminodioxolanones, whose base-induced cyclization afforded the corresponding β-lactams.     

A highly crystalline microporous hybrid organic-inorganic aluminosilicate resembling the AFI-type zeolite

ECS-14, a crystalline microporous hybrid organic-inorganic aluminosilicate, has been synthesized by using 1,4-bis-(triethoxysilyl)-benzene (BTEB) as a source of silica. Its structure contains a system of linear channels with 12-membered ring openings, running along the [001] direction, resembling the pore architecture of the AFI framework type.