Reactive molecular dynamics simulations of organometallic compound W(CO)6 fragmentation

Irradiation- and collision-induced fragmentation studies provide information about geometry, electronic properties and interactions between structural units of various molecular systems. Such knowledge brings insights into irradiation-driven chemistry of molecular systems which is exploited in different technological applications. An accurate atomistic-level simulation of irradiation-driven chemistry requires reliable models of molecular fragmentation which can be verified against mass spectrometry experiments. In this work fragmentation of a tungsten hexacarbonyl, W(CO)$_6$, molecule is studied by means of reactive molecular dynamics simulations. The quantitatively correct fragmentation picture including different fragmentation channels is reproduced. We show that distribution of the deposited energy over all degrees of freedom of the parent molecule leads to thermal evaporation of CO groups and the formation of W(CO)$_n^+$ ($n = 0-5$) fragments. Another type of fragments, WC(CO)$_n^+$ ($n = 0-4$), is produced due to cleavage of a C--O bond as a result of the localized energy deposition. Calculated fragment appearance energies are in good agreement with experimental data. These fragmentation mechanisms have a general physical nature and should take place in radiation-induced fragmentation of different molecular and biomolecular systems.Comment: 11 pages, 6 figures, submitted to European Physical Journal

Calculated energy loss of swift light ions in platinum and gold: importance of the target electronic excitation spectrum

Understanding and predicting the energy loss of swift ions in metals is important for many applications of charged particle beams, such as analysis and modification of materials, and recently for modelling metal nanoparticle radiosensitisation in ion beam cancer therapy. We have calculated the stopping power of the transition metals Pt and Au for protons and alpha particles in a wide energy range, using the dielectric formalism, which realistically accounts for the excitation spectrum of each metal through the Mermin Energy Loss Function - Generalised Oscillator Strength methodology. For each combination of projectile, energy and target, we have considered: (i) the equilibrium charge state of the projectile through the target, (ii) the energy-loss due to electron capture and loss processes, and (iii) the energy loss resulting from the polarisation of the projectile's electronic cloud due to the self-induced electric field. Our calculated stopping powers show a fairly good agreement with the available experimental data for platinum and gold, particularly the most recent ones around the stopping power maximum, which validates the methodology we have used to be further extended to other transition metals. For the materials studied (platinum and gold), two commonly used and different sources of the experimental excitation spectrum yield comparable calculated stopping powers and mean excitation energies, the latter being closer to the most recent data provided in a recent ICRU Report than to previous compilations. Despite the small differences in the sources of excitation spectra of these metals, they lead to practically the same stopping power results as far as they reproduce the main excitation features of the material and fulfil physically motivated sum rules.Comment: 7 pages, 2 figure

Angular and Energy Distributions of Electrons Produced in Arbitrary Biomaterials by Proton Impact

We present a simple method for obtaining reliable angular and energy distributions of electrons ejected from arbitrary condensed biomaterials by proton impact. Relying on a suitable description of the electronic excitation spectrum and a physically motivated relation between the ion and electron scattering angles, it yields cross sections in rather good agreement with experimental data in a broad range of ejection angles and energies, by only using as input the target composition and density. The versatility and simplicity of the method, which can be also extended to other charged particles, make it especially suited for obtaining ionization data for any complex biomaterial present in realistic cellular environments.The authors recognize the financial support from the Spanish Ministerio de Economía y Competitividad and the European Regional Development Fund (Project No. FIS2010–17225). PdV acknowledges financial support from the European Union’s FP7-People Program (Marie Curie Actions) within the Initial Training Network No. 608163 "ARGENT". Support from the European COST Action MP1002 NanoIBCT is gratefully acknowledged

Calculated energy loss of swift light ions in platinum and gold: importance of the target electronic excitation spectrum

Understanding and predicting the energy loss of swift ions in metals is important for many applications of charged particle beams, such as analysis and modification of materials, and recently for modelling metal nanoparticle radiosensitisation in ion beam cancer therapy. We have calculated the stopping power of the transition metals Pt and Au for protons and alpha particles in a wide energy range, using the dielectric formalism, which realistically accounts for the excitation spectrum of each metal through the Mermin Energy Loss Function - Generalised Oscillator Strength methodology. For each combination of projectile, energy and target, we have considered: (i) the equilibrium charge state of the projectile through the target, (ii) the energy-loss due to electron capture and loss processes, and (iii) the energy loss resulting from the polarisation of the projectile's electronic cloud due to the self-induced electric field. Our calculated stopping powers show a fairly good agreement with the available experimental data for platinum and gold, particularly the most recent ones around the stopping power maximum, which validates the methodology we have used to be further extended to other transition metals. For the materials studied (platinum and gold), two commonly used and different sources of the experimental excitation spectrum yield comparable calculated stopping powers and mean excitation energies, the latter being closer to the most recent data provided in a recent ICRU Report than to previous compilations. Despite the small differences in the sources of excitation spectra of these metals, they lead to practically the same stopping power results as far as they reproduce the main excitation features of the material and fulfil physically motivated sum rules.We thank financial support from the European Union's Horizon 2020 Research and Innovation programme under the Marie Sklodowska-Curie grant agreement no. 840752, the Spanish Ministerio de Economía y Competitividad and the European Regional Development Fund (Project no. PGC2018-096788-B-I00), and the Fundación Séneca (Project no. 19907/GERM/15)

Excitation and ionisation cross-sections in condensed-phase biomaterials by electrons down to very low energy: application to liquid water and genetic building blocks

Electronic excitations and ionisations produced by electron impact are key processes in the radiation-induced damage mechanisms in materials of biological relevance, underlying important medical and technological applications, including radiotherapy, radiation protection in manned space missions and nanodevice fabrication techniques. However, experimentally measuring all the necessary electronic interaction cross-sections for every relevant material is an arduous task, so it is necessary having predictive models, sufficiently accurate yet easily implementable. In this work we present a model, based on the dielectric formalism, to provide reliable ionisation and excitation cross-sections for electron-impact on complex biomolecular media, considering their condensed-phase nature. We account for the indistinguishability and exchange between the primary beam and excited electrons, for the molecular electronic structure effects in the electron binding, as well as for low-energy corrections to the first Born approximation. The resulting approach yields total ionisation cross-sections, energy distributions of secondary electrons, and total electronic excitation cross-sections for condensed-phase biomaterials, once the electronic excitation spectrum is known, either from experiments or from a predictive model. The results of this methodology are compared with the available experimental data in water and DNA/RNA molecular building blocks, showing a very good agreement and a great predictive power in a wide range of electron incident energies, from the large values characteristic of electron beams down to excitation threshold. The proposed model constitutes a very useful procedure for computing the electronic interaction cross-sections for arbitrary biological materials in a wide range of electron incident energies.This work has received funding from the European Union's Horizon 2020 Research and Innovation programme under the Marie Sklodowska-Curie grant agreement no. 840752, from the Spanish Ministerio de Economía y Competitividad and the European Regional Development Fund (Project no. PGC2018-096788-B-I00), from the Fundación Séneca (Project no. 19907/GERM/15) and from the Conselleria d'Educació, Investigació, Cultura i Esport de la Generalitat Valenciana (Project no. AICO/2019/070). PdV acknowledges further financial support provided by the Spanish Ministerio de Economía y Competitividad by means of a Juan de la Cierva postdoctoral fellowship (FJCI-2017-32233)

Simulation of the energy spectra of swift light ion beams after traversing cylindrical targets: a consistent interpretation of experimental data relevant for hadron therapy

We have performed detailed simulations of the energy spectra, recorded at several angles, of proton and helium ion beams after traversing thin cylindrical targets of different nature (liquid water and ethanol jets, as well as a solid aluminium wire), in order to reproduce a series of measurements intended to assess the stopping power of 0.3–2 MeV ions. The authors of these experiments derived values of the stopping power of liquid water (a quantity essential for the evaluation of radiation effects in materials, particularly for radiotherapy purposes) that are ~10% lower than what is expected from other measurements and theories. In our simulations, instead of treating the stopping power as an unknown free parameter to be determined, we use as input the electronic stopping power accurately calculated within the dielectric formalism. We take into account in the simulations the different interactions that each projectile can experience when moving through the target, such as electronic stopping, nuclear scattering or electron charge-exchange processes. The detailed geometry of the target is also accounted for. We find that our simulated energy distributions are in excellent agreement with the published measurements when the diameter of the cylindrical targets is slightly reduced, what is compatible with the potential evaporation of the liquid jets. On the basis of such an excellent agreement, we validate the accuracy of the model we use to calculate electronic excitation cross sections for ions in condensed matter in its range of applicability (particularly the electronic stopping power) needed for charged particle transport models, and we offer a consistent, but alternative, interpretation for these experiments on ion irradiation of cylindrical targets.Financial support was provided by the Spanish Ministerio de Economía y Competitividad, the Spanish Ministerio de Ciencia, Innovación y Universidades and the European Regional Development Fund (Projects No. FIS2014-58849-P and PGC2018-096788-B-I00), as well as by the Fundación Séneca - Agencia de Ciencia y Tecnología de la Región de Murcia (Project No. 19907/GERM/15). PdV also acknowledges financial support provided by the Alexander von Humboldt Stiftung/Foundation through a postdoctoral fellowship

Comparative analysis of the secondary electron yield from carbon nanoparticles and pure water medium

The production of secondary electrons generated by carbon nanoparticles and pure water medium irradiated by fast protons is studied by means of model approaches and Monte Carlo simulations. It is demonstrated that due to a prominent collective response to an external field, the nanoparticles embedded in the medium enhance the yield of low-energy electrons. The maximal enhancement is observed for electrons in the energy range where plasmons, which are excited in the nanoparticles, play the dominant role. Electron yield from a solid carbon nanoparticle composed of fullerite, a crystalline form of C60 fullerene, is demonstrated to be several times higher than that from liquid water. Decay of plasmon excitations in carbon-based nanosystems thus represents a mechanism of increase of the low-energy electron yield, similar to the case of sensitizing metal nanoparticles. This observation gives a hint for investigation of novel types of sensitizers to be composed of metallic and organic parts.Comment: 9 pages, 5 figures; accepted for publication in the Topical Issue "COST Action Nano-IBCT: Nano-scale processes behind Ion-Beam Cancer Therapy" of Eur. Phys. J. D. arXiv admin note: text overlap with arXiv:1412.553

Tectonostratigraphic Evolution of the orange basin, sw Africa

The Orange Basin is a Late Jurassic to present day basin located on the volcanic-rifted passive margin of SW Africa. 2D seismic data and structural restoration techniques were used to develop a tectonostratigraphic model of the basin consisting of a syn-rift and a post-rift megasequences separated by an Early Cretaceous break-up unconformity. The post-rift megasequence is characterised by gravity tectonics where extensional faults transferred displacement downdip into a deep water fold and thrust belt (DWFTB). Gravity gliding tectonics occurred through a combination of cratonic uplift and thermal subsidence and stopped via deltaic progradation and associated differential sedimentary loading