Gamma-ray emission from massive young stellar objects

Context.Massive stars form in dense and massive molecular cores. The exact formation mechanism is unclear, but it is possible that some massive stars are formed by processes similar to those that produce the low-mass stars, with accretion/ejection phenomena occurring at some point of the evolution of the protostar. This picture seems to be supported by the detection of a collimated stellar wind emanating from the massive protostar IRAS 16547-4247. A triple radio source is associated with the protostar: a compact core and two radio lobes. The emission of the southern lobe is clearly non-thermal. Such emission is interpreted as synchrotron radiation produced by relativistic electrons locally accelerated at the termination point of a thermal jet. Since the ambient medium is determined by the properties of the molecular cloud in which the whole system is embedded, we can expect high densities of particles and infrared photons. Because of the confirmed presence of relativistic electrons, inverse Compton and relativistic Bremsstrahlung interactions are unavoidable. Aims.We aim to make quantitative predictions of the spectral energy distribution of the non-thermal spots generated by massive young stellar objects, with emphasis on the particular case of IRAS 16547-4247. Methods.We study the high-energy emission generated by the relativistic electrons which produce the non-thermal radio source in IRAS 16547-4247. We also study the result of proton acceleration at the terminal shock of the thermal jet and make estimates of the secondary gamma rays and electron-positron pairs produced by pion decay. Results.We present spectral energy distributions for the southern lobe of IRAS 16547-4247, for a variety of conditions. We show that high-energy emission might be detectable from this object in the gamma-ray domain. The source may also be detectable in X-rays through long exposures with current X-ray instruments. Conclusions.Gamma-ray telescopes such as GLAST, and even ground-based Cherenkov arrays of new generation can be used to study non-thermal processes occurring during the formation of massive stars.

Distorted-wave calculation of cross sections for inner-shell ionization by electron and positron impact

The relativistic distorted-wave Born approximation is used to calculate differential and total cross sections for inner shell ionization of neutral atoms by electron and positron impact. The target atom is described within the independent-electron approximation using the self-consistent Dirac-Fock-Slater potential. The distorting potential for the projectile is also set equal to the Dirac-Fock-Slater potential. For electrons, this guarantees orthogonality of all the orbitals involved and simplifies the calculation of exchange T-matrix elements. The interaction between the projectile and the target electrons is assumed to reduce to the instantaneous Coulomb interaction. The adopted numerical algorithm allows the calculation of differential and total cross sections for projectiles with kinetic energies ranging from the ionization threshold up to about ten times this value. Algorithm accuracy and stability are demonstrated by comparing differential cross sections calculated by our code with the distorting potential set to zero with equivalent results generated by a more robust code that uses the conventional plane-wave Born approximation. Sample calculation results are presented for ionization of K- and L-shells of various elements and compared with the available experimental data.

Optical-model potential for electron and positron elastic scattering by atoms

An optical-model potential for systematic calculations of elastic scattering of electrons and positrons by atoms and positive ions is proposed. The electrostatic interaction is determined from the Dirac-Hartree-Fock self-consistent atomic electron density. In the case of electron projectiles, the exchange interaction is described by means of the local-approximation of Furness and McCarthy. The correlation-polarization potential is obtained by combining the correlation potential derived from the local density approximation with a long-range polarization interaction, which is represented by means of a Buckingham potential with an empirical energy-dependent cutoff parameter. The absorption potential is obtained from the local-density approximation, using the Born-Ochkur approximation and the Lindhard dielectric function to describe the binary collisions with a free-electron gas. The strength of the absorption potential is adjusted by means of an empirical parameter, which has been determined by fitting available absolute elastic differential cross-section data for noble gases and mercury. The Dirac partial-wave analysis with this optical-model potential provides a realistic description of elastic scattering of electrons and positrons with energies in the range from ~100 eV up to ~5 keV. At higher energies, correlation-polarization and absorption corrections are small and the usual static-exchange approximation is sufficiently accurate for most practical purposes.

Electron localization function at the correlated level

The electron localization function (ELF) has been proven so far a valuable tool to determine the location of electron pairs. Because of that, the ELF has been widely used to understand the nature of the chemical bonding and to discuss the mechanism of chemical reactions. Up to now, most applications of the ELF have been performed with monodeterminantal methods and only few attempts to calculate this function for correlated wave functions have been carried out. Here, a formulation of ELF valid for mono- and multiconfigurational wave functions is given and compared with previous recently reported approaches. The method described does not require the use of the homogeneous electron gas to define the ELF, at variance with the ELF definition given by Becke. The effect of the electron correlation in the ELF, introduced by means of configuration interaction with singles and doubles calculations, is discussed in the light of the results derived from a set of atomic and molecular systems

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31 G* and extended 6-31++ G* basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack

PENELOPE-2008: A Code System for Monte Carlo Simulation of Electron and Photon Transport

The computer code system PENELOPE (version 2008) performs Monte Carlo simulation of coupledelectron-photon transport in arbitrary materials for a wide energy range, from a few hundred eV toabout 1 GeV. Photon transport is simulated by means of the standard, detailed simulation scheme.Electron and positron histories are generated on the basis of a mixed procedure, which combinesdetailed simulation of hard events with condensed simulation of soft interactions. A geometry packagecalled PENGEOM permits the generation of random electron-photon showers in material systemsconsisting of homogeneous bodies limited by quadric surfaces, i.e., planes, spheres, cylinders, etc. Thisreport is intended not only to serve as a manual of the PENELOPE code system, but also to provide theuser with the necessary information to understand the details of the Monte Carlo algorithm.

The effects of electron-hole separation on the photoconductivity of individual metal oxide nanowires

The responses of individual ZnO nanowires to UV light demonstrate that the persistent photoconductivity (PPC) state is directly related to the electron¿hole separation near the surface. Our results demonstrate that the electrical transport in these nanomaterials is influenced by the surface in two different ways. On the one hand, the effective mobility and the density of free carriers are determined by recombination mechanisms assisted by the oxidizing molecules in air. This phenomenon can also be blocked by surface passivation. On the other hand, the surface built-in potential separates the photogenerated electron¿hole pairs and accumulates holes at the surface. After illumination, the charge separation makes the electron¿hole recombination difficult and originates PPC. This effect is quickly reverted after increasing either the probing current (self-heating by Joule dissipation) or the oxygen content in air (favouring the surface recombination mechanisms). The model for PPC in individual nanowires presented here illustrates the intrinsic potential of metal oxide nanowires to develop optoelectronic devices or optochemical sensors with better and new performances.

Disseny i optimització de membranes compòsit amb xarxes metal•loorgàniques per a nanofiltració i separacions de gasos

Projecte de recerca elaborat a partir d’una estada a la Katholieke Universiteit Leuven, Belgium, entre 2007 i 2009. Aquest projecte descriu la síntesi i aplicació de nous tipus de membranes compòsit basades en xarxes metal•loorgàniques (MOFs). Aquestes es van seleccionar tenint en compte les seves propietats estructurals per tal de discriminar les espècies a separar en funció de la seva mida molecular. Les membranes obtingudes s'han aplicat satisfactòriament tant en separacions líquides, concretament en nanofiltració resistent a dissolvents (SRNF), i en separació de parells de gasos com CO2/CH4, CO2/N2 i H2/CO2. Els resultats obtinguts posen de manifest l'obtenció de membranes sense defectes i amb rendiments prometedors, en la majoria dels casos, amb permeabilitats i selectivitats superiors a membranes purament polimèriques. Tanmateix s'ha desenvolupat un nou equipament d'alt rendiment (HT) per a separacions de gasos que inclou un mòdul que permet realitzar 16 experiments simultàniament. Els resultats obtinguts amb el nou equip són comparables amb els obtinguts amb mòduls convencionals, i alhora presenten una millor reproduïbilitat. Finalment, s'ha establert un nou mètode per a obtenir membranes per a SRNF, que han estat aplicades en processos de separació de catalitzadors homogenis en dissolvents polars apròtics i s'han caracteritzat emprant la tècnica d'espectroscòpia d'annihilació de positrons, que ha permès establir per primer cop una relació entre les propietats estructurals de les membranes a nivell molecular i el seu rendiment en les aplicacions anteriors.

The relevance of the Laplacian of intracule and extracule density distributions for analyzing electron-electron interactions in molecules

A topological analysis of intracule and extracule densities and their Laplacians computed within the Hartree-Fock approximation is presented. The analysis of the density distributions reveals that among all possible electron-electron interactions in atoms and between atoms in molecules only very few are located rigorously as local maxima. In contrast, they are clearly identified as local minima in the topology of Laplacian maps. The conceptually different interpretation of intracule and extracule maps is also discussed in detail. An application example to the C2H2, C2H4, and C2H6 series of molecules is presented

A chemical Hamiltonian approach study of the basis set superposition error changes on electron densities and one- and two-center energy components

A comparision of the local effects of the basis set superposition error (BSSE) on the electron densities and energy components of three representative H-bonded complexes was carried out. The electron densities were obtained with Hartee-Fock and density functional theory versions of the chemical Hamiltonian approach (CHA) methodology. It was shown that the effects of the BSSE were common for all complexes studied. The electron density difference maps and the chemical energy component analysis (CECA) analysis confirmed that the local effects of the BSSE were different when diffuse functions were present in the calculations

Effect of basis set superposition error on the electron density of molecular complexes

The effect of basis set superposition error (BSSE) on molecular complexes is analyzed. The BSSE causes artificial delocalizations which modify the first order electron density. The mechanism of this effect is assessed for the hydrogen fluoride dimer with several basis sets. The BSSE-corrected first-order electron density is obtained using the chemical Hamiltonian approach versions of the Roothaan and Kohn-Sham equations. The corrected densities are compared to uncorrected densities based on the charge density critical points. Contour difference maps between BSSE-corrected and uncorrected densities on the molecular plane are also plotted to gain insight into the effects of BSSE correction on the electron density

A quantum molecular similarity analysis of changes in molecular electron density caused by basis set flotation and electric field application

Quantum molecular similarity (QMS) techniques are used to assess the response of the electron density of various small molecules to application of a static, uniform electric field. Likewise, QMS is used to analyze the changes in electron density generated by the process of floating a basis set. The results obtained show an interrelation between the floating process, the optimum geometry, and the presence of an external field. Cases involving the Le Chatelier principle are discussed, and an insight on the changes of bond critical point properties, self-similarity values and density differences is performed

Basis set and electron correlation effects on initial convergence for vibrational nonlinear optical properties of conjugated organic molecules

The level of ab initio theory which is necessary to compute reliable values for the static and dynamic (hyper)polarizabilities of three medium size π-conjugated organic nonlinear optical (NLO) molecules is investigated. With the employment of field-induced coordinates in combination with a finite field procedure, the calculations were made possible. It is stated that to obtain reasonable values for the various individual contributions to the (hyper)polarizability, it is necessary to include electron correlation. Based on the results, the convergence of the usual perturbation treatment for vibrational anharmonicity was examined

Electronic couplings and on-site energies for hole transfer in DNA: systematic quantum mechanical/molecular dynamic study

The electron hole transfer (HT) properties of DNA are substantially affected by thermal fluctuations of the π stack structure. Depending on the mutual position of neighboring nucleobases, electronic coupling V may change by several orders of magnitude. In the present paper, we report the results of systematic QM/molecular dynamic (MD) calculations of the electronic couplings and on-site energies for the hole transfer. Based on 15 ns MD trajectories for several DNA oligomers, we calculate the average coupling squares 〈 V2 〉 and the energies of basepair triplets X G+ Y and X A+ Y, where X, Y=G, A, T, and C. For each of the 32 systems, 15 000 conformations separated by 1 ps are considered. The three-state generalized Mulliken-Hush method is used to derive electronic couplings for HT between neighboring basepairs. The adiabatic energies and dipole moment matrix elements are computed within the INDO/S method. We compare the rms values of V with the couplings estimated for the idealized B -DNA structure and show that in several important cases the couplings calculated for the idealized B -DNA structure are considerably underestimated. The rms values for intrastrand couplings G-G, A-A, G-A, and A-G are found to be similar, ∼0.07 eV, while the interstrand couplings are quite different. The energies of hole states G+ and A+ in the stack depend on the nature of the neighboring pairs. The X G+ Y are by 0.5 eV more stable than X A+ Y. The thermal fluctuations of the DNA structure facilitate the HT process from guanine to adenine. The tabulated couplings and on-site energies can be used as reference parameters in theoretical and computational studies of HT processes in DNA

Electron capture and emission by the Ti acceptor level in GaP

Previously reported results on deep level optical spectroscopy, optical absorption, deep level transient spectroscopy, photoluminescence excitation, and time resolved photoluminescence are reviewed and discussed in order to know which are the mechanisms involved in electron capture and emission of the Ti acceptor level in GaP. First, the analysis indicates that the 3T1(F) crystal¿field excited state is not in resonance with the conduction band states. Second, it is shown that both the 3T2 and 3T1(F) excited states do not play any significant role in the process of electron emission and capture.