R-matrix calculations of low-energy electron alkane collisions

Ab initio electron scattering calculations are presented for methane, ethane and propane with particular emphasis on elastic cross sections. Calculations are performed with the Quantemol-N expert system which runs the UK polyatomic R-matrix code. These calculations are presented which systematically increase the size of the coupled states expansion which is used to represent polarisation effects in the scattering wave function. Agreement with experimental measurements is obtained provided sufficient coupled states are included in the expansion. Whether these coupled states expansions really converge the polarisation potential and the prospects for further calculations are discussed. (c) 2007 Elsevier B.V. All rights reserved

R-matrix calculations on molecules of astrophysical interest using Quantemol-N

We have carried out a series of ab initio R-matrix calculations at the static exchange and close-coupling levels of approximation on molecules of astrophysical interest. These include the polar triatomics HCN and HNC (hydrogen isocyanide) and their isotopologues DCN and DNC, the diatomics CS (carbon monosulphide) and SiO (silicon monoxide), the weakly polar CO molecule and the non-polar CH4 molecule. With the exception of CO, all the calculations presented here were carried out using the software ‘Quantemol-N’ which provides an intuitive user-friendly interface to the UK polyatomic R-matrix codes. A chapter is devoted to the discussion on the software: how to prepare an R-matrix calculation using it, its present capabilities and future development. The ultimate aim of this thesis is to demonstrate the need to account for electron-induced chemistry in any astrophysical model. We seek to show that in the case of polar molecules, namely, those molecules with large dipole moments, electron collisions are the dominant mechanism of rotational excitation in comets and other astrophysical bodies. Specifically, we will show that electron-impact excitation rate coefficients are several orders of magnitude higher than the corresponding atom-molecule ones. The thesis concludes with a summary of the key findings and opportunities (and where necessary improvements) that may arise from them. All the scattering equations presented here used atomic units

CROSS SECTIONS FOR SCATTERING OF ELECTRONS ON BF3

We calculate cross sections for elastic scattering and electronic excitation of BF3 molecules by low energy electrons. The R-Matrix code Quantemol-N has been used for calculations. The cross sections indicate the presence of a shape resonance of symmetry B-1 (A(2)'' in D-3h) at around 4.5 eV

Electron-impact rotational and hyperfine excitation of HCN, HNC, DCN and DNC

Rotational excitation of isotopologues of HCN and HNC by thermal electron-impact is studied using the molecular {\bf R}-matrix method combined with the adiabatic-nuclei-rotation (ANR) approximation. Rate coefficients are obtained for electron temperatures in the range 5$-$6000 K and for transitions among all levels up to J=8. Hyperfine rates are also derived using the infinite-order-sudden (IOS) scaling method. It is shown that the dominant rotational transitions are dipole allowed, that is those for which $\Delta J=1$. The hyperfine propensity rule $\Delta J=\Delta F$ is found to be stronger than in the case of He$-$HCN collisions. For dipole allowed transitions, electron-impact rates are shown to exceed those for excitation of HCN by He atoms by 6 orders of magnitude. As a result, the present rates should be included in any detailed population model of isotopologues of HCN and HNC in sources where the electron fraction is larger than 10$^{-6}$, for example in interstellar shocks and comets.Comment: 12 pages, 4 figures, accepted in MNRAS (2007 september 3

The magnetic precursor of L1448-mm: Excitation differences between ion and neutral fluids

Shock modelling predicts an electron density enhancement within the magnetic precursor of C-shocks. Previous observations of SiO, H13CO+, HN13C and H13CN toward the young L1448-mm outflow showed an over-excitation of the ion fluid that was attributed to an electron density enhancement in the precursor. We re-visit this interpretation and test if it still holds when we consider different source morphologies and kinetic temperatures for the observed molecules, and also give some insight on the spatial extent of the electron density enhancement around L1448-mm. We estimate the opacities of H13CO+ and HN13C by observing the J=3\to2 lines of rarer isotopologues to confirm that the emission is optically thin. To model the excitation of the molecules, we use the large velocity gradient (LVG) approximation with updated collisional coefficients to i) re- analyse the observations toward the positions where the over-excitation of H13CO+ has previously been observed [i.e. toward L1448- mm at offsets (0,0) and (0,-10)], and ii) to investigate if the electron density enhancement is still required for the cases of extended and compact emission, and for kinetic temperatures of up to 400 K. We also report several lines of SiO, HN13C and H13CO+ toward new positions around this outflow, to investigate the spatial extent of the over-excitation of the ions in L1448-mm. From the isotopologue observations, we find that the emission of H13CO+ and HN13C from the precursor is optically thin if this emission is extended. Using the new collisional coefficients, an electron density enhancement is still needed to explain the excitation of H13CO+ for extended emission and for gas temperatures of\le 400 K toward L1448-mm (0,-10), and possibly also toward L1448-mm (0,0). For compact emission the data cannot be fitted. We do not find any evidence for the over-excitation of the ion fluid toward the newly observed positions around L1448-mm. The observed line emission of SiO, H13CO+ and HN13C toward L1448-mm (0,0) and (0,-10) is consistent with an electron density enhancement in the precursor component, if this emission is spatially extended. This is also true for the case of high gas temperatures (\le400 K) toward the (0,-10) offset. The electron density enhancement seems to be restricted to the southern, redshifted lobe of the L1448-mm outflow. Interferometric images of the line emission of these molecules are needed to confirm the spatial extent of the over-excitation of the ions and thus, of the electron density enhancement in the magnetic precursor of L1448-mm.Comment: Accepted for publication in A&A; 9 pages, 3 figure

Quantemol-N: an expert system for performing electron molecule collision calculations using the R-matrix method

The R-matrix method has been widely employed to ab initio calculations on a large variety of problems related to electron molecule scattering. The UK Molecular R-matrix Code, which are a synthesis between codes designed for quantum chemistry and electron atom scattering calculations, has proved particularly popular for these studies but is difficult for the non-specialist to use. The Quantemol-N software environment is designed for scientists with a minimal knowledge of scattering theory or quantum chemistry to use without the need of a complex and dedicated training. Their use is illustrated for low energy electron collisions with silane

Managing dose-, damage- and data-rates in multi-frame spectrum-imaging

As an instrument, the scanning transmission electron microscope is unique in being able to simultaneously explore both local structural and chemical variations in materials at the atomic scale. This is made possible as both types of data are acquired serially, originating simultaneously from sample interactions with a sharply focused electron probe. Unfortunately, such scanned data can be distorted by environmental factors, though recently fast-scanned multi-frame imaging approaches have been shown to mitigate these effects. Here, we demonstrate the same approach but optimized for spectroscopic data; we offer some perspectives on the new potential of multi-frame spectrum-imaging (MFSI) and show how dose-sharing approaches can reduce sample damage, improve crystallographic fidelity, increase data signal-to-noise, or maximize usable field of view. Further, we discuss the potential issue of excessive data-rates in MFSI, and demonstrate a file-compression approach to significantly reduce data storage and transmission burdens

Targeted T1 Magnetic Resonance Imaging Contrast Enhancement with Extraordinarily Small CoFe2O4 Nanoparticles

Extraordinarily small (2.4 nm) cobalt ferrite nanoparticles (ESCIoNs) were synthesized by a one-pot thermal decomposition approach to study their potential as magnetic resonance imaging (MRI) contrast agents. Fine size control was achieved using oleylamine alone, and annular dark-field scanning transmission electron microscopy revealed highly crystalline cubic spinel particles with atomic resolution. Ligand exchange with dimercaptosuccinic acid rendered the particles stable in physiological conditions with a hydrodynamic diameter of 12 nm. The particles displayed superparamagnetic properties and a low r2/r1 ratio suitable for a T1 contrast agent. The particles were functionalized with bile acid, which improved biocompatibility by significant reduction of reactive oxygen species generation and is a first step toward liver-targeted T1 MRI. Our study demonstrates the potential of ESCIoNs as T1 MRI contrast agents