Suppression of multiple ionization of atomic ions in intense ultrafast laser pulses

The interaction of an intense laser field with a beam of atomic ions has been investigated experimentally for the first time. The ionization dynamics of Ar+ ions and Ar neutrals in a 60 fs, 790 nm laser pulse have been compared and contrasted at intensities up to 10(16) W cm (-2). Our results show that nonsequential ionization from an Ar+ target is strongly suppressed compared with that from the corresponding neutral target. We have also observed for the first time the strong field ionization of high lying target metastable levels in the Ar+ beam.

Energy analysis of hyperthermal hydrogen atoms generated through surface neutralisation of ions

Hydrogen ions (H+, H-2(+) and H-3(+)) are produced in a magnetically confined inductively coupled radio frequency plasma. Ions are accelerated in the plasma boundary sheath potential, of several hundred volts, in front of a biased metal electrode immersed in the plasma. Backscattered hyperthermal hydrogen atoms are investigated by optical emission spectroscopy and an energy-resolved mass spectrometer. Ionisation of fast neutrals through electron stripping of atoms in the plasma allows energy analysis of the resulting ions. Thereby, the energy distribution function of the hyperthermal atoms can be deduced. The energy spectra can be explained as a superposition of individual spectra of the various ion species. The measured spectra also shows contributions of negative ions created at the electrode surface. In addition to experimental measurements, simulations of the neutral flux of backscattered atoms are carried out.

Prediction of the formation and stabilities of energetic salts and ionic liquids based on ab initio electronic structure calculations

A computational approach to predict the thermodynamics for forming a variety of imidazolium-based salts and ionic liquids from typical starting materials is described. The gas-phase proton and methyl cation acidities of several protonating and methylating agents, as well as the proton and methyl cation affinities of many important methyl-, nitro-, and cyano- substituted imidazoles, have been calculated reliably by using the computationally feasible DFT (B3LYP) and MP2 (extrapolated to the complete basis set limit) methods. These accurately calculated proton and methyl cation affinities of neutrals and anions are used in conjunction with an empirical approach based on molecular volumes to estimate the lattice enthalpies and entropies of ionic liquids, organic solids, and organic liquids. These quantities were used to construct a thermodynamic cycle for salt formation to reliably predict the ability to synthesize a variety of salts including ones with potentially high energetic densities. An adjustment of the gas phase thermodynamic cycle to account for solid- and liquid-phase chemistries provides the best overall assessment of salt formation and stability. This has been applied to imidazoles (the cation to be formed) with alkyl, nitro, and cyano substituents. The proton and methyl cation donors studied were as follows: HCl, HBr, HI, (HO)(2)SO2, HSO3CF3 (TfOH), and HSO3(C6H4)CH3 (TsOH); CH3Cl, CH3Br, CH3I, (CH3O)(2)SO2, CH3SO3CF3 (TfOCH3) and CH3SO3(C6H4)CH3 (TsOCH3). As substitution of the cation with electron-withdrawing groups increases, the triflate reagents appear to be the best overall choice as protonating and methylating agents. Even stronger alkylating agents should be considered to enhance the chances of synthetic success. When using the enthalpies of reaction for the gas-phase reactants (eq 6) to form a salt, a cutoff value of - 13 kcal mol(-1) or lower (more negative) should be used as the minimum value for predicting whether a salt can be synthesized.

Three dimensional number density mapping in the plume of a low temperature laser ablated magnesium plasma

Simultaneous optical absorption and laser-induced fluorescence measurements have been used to map the three-dimensional number densities of ground-state ions and neutrals within a low-temperature KrF laser-produced magnesium plasma expanding into vacuum. Data is reported for the symmetry plane of the plasma, which includes the laser interaction point at a delay of 1 μs after the ∼30 ns KrF laser ablation pulse and for a laser fluence of 2 J cm−2 on target. The number density distributions of ion and neutral species within this plane indicate that two distinct regions exist within the plume; one is a fast component containing ions and neutrals at maximum densities of ∼3×1013 cm−3 and ∼4×1012 cm−3, respectively and the second is a high-density region containing slow neutral species, at densities up to ∼1×1015 cm−3.

Electron-impact rotational excitation of the carbon monosulphide (CS) molecule

Rotational excitation of the carbon monosulphide (CS) molecule by thermal electron-impact is studied using the molecular R-matrix method combined with the adiabatic-nuclei-rotation (ANR) approximation. Rate coefficients are obtained for electron temperatures in the range 5-5000 K and for transitions involving levels up to J = 40. It is confirmed that dipole allowed transitions (Delta J = 1) are dominant and that the corresponding rate coefficients exceed those for excitation by neutrals by at least five orders of magnitude. As a result, the present rates should be included in any detailed population model of CS in sources where the electron fraction is larger than similar to 10(-5), in particular in diffuse molecular clouds and interstellar shocks.

THE CHEMISTRY OF PAH AND FULLERENE MOLECULES IN INTERSTELLAR CLOUDS

Recent laboratory data on the ion-neutral chemistry of PAH and fullerene ions and molecules have been incorporated into chemical kinetic models of interstellar clouds. The laboratory data show that the-second ionization potentials of many complex molecules are less than the first ionization potential of helium. Thus collisions between He+, generated by cosmic ray ionization, and PAH and fullerene neutrals produce doubly charged cations. I find that these cations, and also protonated neutrals, are abundant in dark clouds. If the recombination of electrons with doubly charged cations, which releases typically 14 eV of energy, is dissociative in nature, then PAH and fullerene species are destroyed m both diffuse and dense clouds on astronomically significant time-scales.

MeV negative ion source from ultra-intense laser-matter interaction

Experimental demonstration of negative ion acceleration to MeV energies from sub-micron size droplets of water spray irradiated by ultra-intense laser pulses is presented. Thanks to the specific target configuration and laser parameters, more than 109 negative ions per steradian solid angle in 5% energy bandwidth are accelerated in a stable and reliable manner. To our knowledge, by virtue of the ultra-short duration of the emission, this is by far the brightest negative ion source reported. The data also indicate the existence of beams of neutrals with at least similar numbers and energies.

Proton irradiation of DNA nucleosides in the gas phase

The four DNA nucleosides guanosine, adenosine, cytidine and thymidine have been produced in the gas phase by a laser thermal desorption source, and irradiated by a beam of protons with 5 keV kinetic energy. The molecular ions as well as energetic neutrals formed have been analyzed by mass spectrometry in order to shed light on the ionization and fragmentation processes triggered by proton collision. A range of 8-20 eV has been estimated for the binding energy of the electron captured by the proton. Glycosidic bond cleavage between the base and sugar has been observed with a high probability for all nucleosides, resulting in predominantly intact base ions for guanosine, adenosine, and cytidine but not for thymidine where intact sugar ions are dominant. This behavior is influenced by the ionization energies of the nucleobases (G < A < C < T), which seems to determine the localization of the charge following the initial ionization. This charge transfer process can also be inferred from the production of protonated base ions, which have a similar dependence on the base ionization potential. Other dissociation pathways have also been identified, including further fragmentation of the base and sugar moieties for thymidine and guanosine, respectively, and partial breakup of the sugar ring without glycosidic bond cleavage mainly for adenosine and cytidine. These results show that charge localization following ionization by proton irradiation is important in determining dissociation pathways of isolated nucleosides, which could in turn influence direct radiation damage in DNA.

Mapping neutral, ion and electron number densities within laser ablated plasma plumes

Spatially and temporally varying neutral, ion and electron number densities have been mapped out within laser ablated plasma plumes expanding into vacuum. Ablation of a magnesium target was performed using a KrF laser, 30 ns pulse duration and 248 nm wavelength. During the initial stage of plasma expansion (t <EQ 100 ns) interferometry has been used to obtain line averaged electron number densities, for laser power densities on target in the range 1.3 - 3.0 X 108 W/cm2. Later in the plasma expansion (t equals 1 microsecond(s) ) simultaneous absorption and laser induced fluorescence spectroscopy has been used to determine 3D neutral and ion number densities, for a power density equal to 6.7 X 107 W/cm2. Two distinct regions within the plume were identified. One is a fast component (approximately 106 cm-1) consisting of ions and neutrals with maximum number densities observed to be approximately 30 and 4 X 1012 cm-3 respectively, and the second consists of slow moving neutral material at a number density of up to 1015 cm-3. Additionally a Langmuir probe has been used to obtain ion and electron number densities at very late times in the plasma expansion (1 microsecond(s) <EQ t <EQ 15 microsecond(s) ). A copper target was ablated using a Nd:YAG laser, 7.5 ns duration and 532 nm (2 (omega) ) wavelength, with a power density on target equal to 6 X 108 W/cm2. Two regions within the plume with different velocities were observed. Within a fast component (approximately 3 X 106 cms-1) electron and ion number densities of the order 5 X 1012 cm-3 were observed and within the second slower component (approximately 106 cms-1) electron and ion number densities of the order 1 - 2 X 1013 cm-3 were determined.

Astrochemistry

In the last 40 years a wide range of molecules, including neutrals, cations and anions, containing up to 13 atoms—in addition to detections of C₆₀ and C₇₀ — have been found in the harsh environment of the interstellar medium. The exquisite sensitivity and very high spectral and, more recently, spatial resolution, of modern telescopes has enabled the physics of star formation to be probed through rotational line emission. In this article, I review the basic properties of interstellar clouds and the processes that initiate the chemistry and generate chemical complexity, particularly in regions of star and planet formation. Our understanding of astrochemistry has evolved over the years. Before 1990, the general consensus was that molecules were formed in binary, gas-phase, or volume, reactions, most importantly ion-neutral reactions despite the very low ionization in clouds. Since then, observations have indicated unambiguously that there is also a contribution from surface processes, particularly on the icy mantles that form around refractory grain cores in cold, dense gas. The balance between these two processes depends on particular physical conditions and can vary during the life cycle of a particular volume of interstellar cloud.The complex chemistry that occurs in space is driven mostly through interaction of thegas with cosmic ray protons, a source of ionization that enables a rich ion-neutral chemistry. In addition, I show that the interaction between the gas and the dust in cold, dense regionsalso leads to additional chemical complexity through reactions that take place in ices at onlya few tens of degrees above absolute zero. Although densities are low compared to those in terrestrial environments, the extremely long life times of interstellar clouds and their enormous sizes, enable complex molecules to be synthesised and detected. I show that in some instances, particularly in reactions involving deuterium, the rotational populations of reactants, together with spin-selection rules, can determine the detailed abundances. Although the review is mainly focused on regions associated with star formation, I also consider chemistry in other interesting astronomical regions — in the early Universe and in the envelopes formed by mass loss during the final stages of stellar evolution.

Chemistry and Distribution of Daughter Species in the Circumstellar Envelopes of O-Rich AGB Stars

Context. Thanks to the advent of Herschel and ALMA, new high-quality observations of molecules present in the circumstellar envelopes of asymptotic giant branch (AGB) stars are being reported that reveal large differences from the existing chemical models. New molecular data and more comprehensive models of the chemistry in circumstellar envelopes are now available.
Aims: The aims are to determine and study the important formation and destruction pathways in the envelopes of O-rich AGB stars and to provide more reliable predictions of abundances, column densities, and radial distributions for potentially detectable species with physical conditions applicable to the envelope surrounding IK Tau.
Methods: We use a large gas-phase chemical model of an AGB envelope including the effects of CO and N2 self-shielding in a spherical geometry and a newly compiled list of inner-circumstellar envelope parent species derived from detailed modeling and observations. We trace the dominant chemistry in the expanding envelope and investigate the chemistry as a probe for the physics of the AGB phase by studying variations of abundances with mass-loss rates and expansion velocities.
Results: We find a pattern of daughter molecules forming from the photodissociation products of parent species with contributions from ion-neutral abstraction and dissociative recombination. The chemistry in the outer zones differs from that in traditional PDRs in that photoionization of daughter species plays a significant role. With the proper treatment of self-shielding, the N → N2 and C+→ CO transitions are shifted outward by factors of 7 and 2, respectively, compared with earlier models. An upper limit on the abundance of CH4 as a parent species of (≲2.5 × 10-6 with respect to H2) is found for IK Tau, and several potentially observable molecules with relatively simple chemical links to other parent species are determined. The assumed stellar mass-loss rate, in particular, has an impact on the calculated abundances of cations and the peak-abundance radius of both cations and neutrals: as the mass-loss rate increases, the peak abundance of cations generally decreases and the peak-abundance radius of all species moves outwards. The effects of varying the envelope expansion velocity and cosmic-ray ionization rate are not as significant.