H3+ in the diffuse interstellar medium

Three forms of solely hydrogen-bearing molecules--H2, HD and H3+--are observed in diffuse or optically transparent interstellar clouds. Although no comprehensive theory exists for the diffuse interstellar medium or its chemistry, the abundances of these species can generally be accommodated locally within the existing static equilibrium frameworks for heating/cooling, H2-formation on large grains, etc. with one modification demanded equally by observations of HD and H3+, i.e. a pervasive low-level source of H and H2 ionization ca 10 times faster than the usual cosmic ray ionization rate zetaH = 10(-17) s(-1) per free H-atom. We discuss this situation with reference to observation and time-dependent modelling of H2 and H3+ formation. While not wishing to appear ungrateful for the success of what are very simplistic notions of the interstellar medium, we point out several reasons not to feel smug. The equilibrium conditions which foster high H2 and H3+ abundances are very slow to appear and these same simple ideas of static equilibrium cannot explain any, but a few, of the simplest of the trace species, which are ubiquitously embedded in H2-bearing diffuse gases.     

H3+ towards and within the Galactic centre

High-resolution spectroscopy of bright infrared sources in the centre of the Galaxy has resulted in the detection of H3+ in a remarkable array of dense and diffuse clouds along the 8000 parsec long line of sight, at a wide range of distances from the centre. Most prominent among these is a previously undetected, but very large amount of warm (T approximately 250 K) and diffuse (n approximately 100 cm2) gas within a few hundred parsecs of the centre. The key to understanding the environment of the H3+ in this region is an H3+ absorption line at 3.53 microm from the metastable (3,3) rotational level, which has not been detected in dense or diffuse clouds outside of the Galactic centre (GC). We have used spectroscopy of this line along with other lines of H3+ and CO to characterize all of the clouds along the line of sight to the GC. The high abundance of H3+ in the central few hundred parsecs implies an ionization rate there that is several times larger than estimated for diffuse clouds outside the GC, and nearly two orders of magnitude greater than originally predicted for diffuse clouds.     

Theoretical progress and challenges in H3+ dissociative recombination

We discuss the Jahn-Teller mechanism for dissociative recombination in low energy collisions between electrons and H3+ ions, in energy ranges relevant to the processes underway in interstellar clouds. While theory has become capable of predicting recombination rates in reasonable agreement with storage ring experiments, some discrepancies remain with them, and a long-standing discrepancy with stationary afterglow measurements remains troubling. Speculations about the desirable improvements in both theory and experiment are presented.     

H3+ cooling in primordial gas

Simulations of the thermal and dynamical evolution of primordial gas typically focus on the role played by H2 cooling. H2 is the dominant coolant in low-density primordial gas and it is usually assumed that it remains dominant at high densities. However, H2 is not an effective coolant at high densities, owing to the low critical density at which it reaches local thermodynamic equilibrium and to the large opacities that develop in its emission lines. It is therefore important to quantify the contribution made to the cooling rate by emission from the other molecules and ions present in the gas. A particularly interesting candidate is the H3+ ion, which is known to be an effective coolant at high densities in planetary atmospheres. In this paper, we present results from simulations of the thermal and chemical evolution of gravitationally collapsing primordial gas, which include a detailed treatment of H3+ chemistry and an approximate treatment of H3+ cooling. We show that in most cases, the contribution from H3+ is too small to be important, but if a sufficiently strong ionizing background is present, then H3+ cooling may become significant.     

Deuterium enhancement in H3+ in pre-stellar cores

Deuterium enhancement of monodeuterated species has been recognized for more than 30 years as a result of chemical fractionation that results from the difference in zero-point energies of deuterated and hydrogenated molecules. The key reaction is the deuteron exchange in the reaction between HD, the reservoir of deuterium in dark interstellar clouds, and the H3+ molecular ion, leading to the production of H2D+ molecule, and the low temperature in dark interstellar clouds favours this production. Furthermore, the presence of multiply deuterated species have incited our group to proceed further and consider the subsequent reaction of H2D+ with HD, leading to D2H+, which can further react with HD to produce D3+. In pre-stellar cores, where CO was found to be depleted, this production should be increased as CO would normally destroy H3+. The first model including D2H+ and D3+ predicted that these molecules should be as abundant as H2D+. The first detection of the D2H+ was made possible by the recent laboratory measurement for the frequency of the fundamental line of para-D2H+. Here, we present observations of H2D+ and D2H+ towards a sample of dark clouds and pre-stellar cores and show how the distribution of ortho-H2D+ (1(1,0)-1(1,1)) can trace the deuterium factory in pre-stellar cores. We also present how future instrumentation will improve our knowledge concerning the deuterium enhancement of H3+.     

Electron-impact rotational excitation of H3+: relevance for thermalization and dissociation dynamics

Electrons are known to be efficient in rotationally exciting molecular ions in low-density astrophysical plasmas. Rotational excitation of molecular ions has also been shown to affect the measured values of dissociative recombination (DR) rate coefficients. Thus, electron collisions with H3+ are expected to play a significant role in thermalization and dissociation dynamics of this ion, both in the laboratory and in space. Using the molecular R-matrix method combined with the adiabatic-nuclei-rotation approximation, we have computed new rate coefficients for the rotational excitation of H3+ by electrons at temperatures from 10 to 10,000 K. De-excitation rates are found to amount to a few 10(-7) cm3 s(-1) below 1000 K, i.e. comparable in magnitude to that of DR. In astrophysical environments where the electron fraction exceeds 10(-4), electron collisions are thus expected to contribute to the non-thermal rotational distribution of H3+. The competition between electron and neutral collisions is discussed in the context of recent observations of H3+ towards Galactic centre sources.     

Deuterated H3+ as a probe of isotope fractionation in star-forming regions

Observations of molecular D/H ratios in the interstellar medium are used to probe the physical conditions, such as temperature, ionization fraction and the importance of gas-grain reactions. In cold, dense regions, such as cores which are collapsing to form stars, the level of deuterium fractionation depends on the conversion of H3+ into its deuterated isotopologues (H2D+, D2H+ and D3+). The relative abundances of these molecules uniquely probe the centres of these cores where other, heavier, species have frozen onto dust grains. We present models of the deuterium chemistry close to the centre of a pre-stellar core, in the last stage before the star forms, showing the dependence of the observable molecular D/H ratios on the physical parameters and rate coefficients that are assumed. We compare model predictions with the latest observations of these regions.     

Using H3+ and H2D+ as probes of star-forming regions

The H3+ and H2D+ ions are important probes of the physical and chemical conditions in regions of the interstellar medium where new stars are forming. This paper reviews how observations of these species and of heavier ions such as HCO+ and H3O+ can be used to derive chemical and kinematic properties of nearby pre-stellar cores and the cosmic ray ionization rate towards more distant regions of high-mass star formation. Future prospects in the field are outlined at the end.     

Submillimetre-wave lines of H2D+ and D2H+ as probes into chemistry in cold dark clouds

We discuss past and recent progress of our continuing project of submillimetre-wave spectroscopic investigations of H2D+ and D2H+. Three new lines of H2D+ in the 2.5-3.5 THz range are measured with a tunable far-infrared laser system. Since these molecules are very light asymmetric molecules, analysis based on a conventional effective Hamiltonian is not very useful in predicting the transition frequencies to the accuracy of the order of several MHz or better. In this respect, any addition of new accurate measurements of transition frequencies is important. In this paper, some discussions will be made on H5+ and its deuterated species as probable interstellar species in cold dark clouds. In particular, D3+, which is predicted to be abundant in cold dark clouds, can be (indirectly) detected by observing D3+ x H2.     

铈离子对高强铝合金应力腐蚀开裂的缓蚀作用

基于慢应变速率拉伸实验(SSRT),采用恒电流极化、电化学噪声(ECN)与电化学阻抗(EIS)等方法,研究7A04铝合金在3.5%(质量分数)NaCl水溶液中的应力腐蚀开裂(SCC)行为以及Ce~(3+)对其SCC的缓蚀作用,探讨Ce~(3+)对裂纹孕育与发展过程的抑制机理。结果表明:无论是阳极还是阴极极化,均会促进7A04的SCC倾向,前者增加了裂尖的阳极溶解,后者则加速了裂尖的氢脆效应。Ce~(3+)的加入能延缓7A04的SCC断裂时间,但其有效性仅限于裂纹的萌生阶段。由于Ce~(3+)能够抑制铝合金表面的亚稳态点蚀发育和长大,因而使裂纹的孕育时间显著延长,降低了SCC的敏感性。不过一旦裂纹进入扩展阶段或者试样表面有预裂纹,则由于Ce~(3+)很难迁移到裂纹尖端或在裂尖区难以成膜,不能对裂纹的生长起到有效抑制作用,因而无法降低7A04的SCC发展速率。SEM分析表明7A04铝合金光滑试样SCC主要源于亚稳态或稳态点蚀的诱导作用。     

Charge-state-dependent sequence analysis of protonated ubiquitin ions via ion trap tandem mass spectrometry

One of the major factors governing the "top-down" sequence analysis of intact multiply protonated proteins by tandem mass spectrometry is the effect of the precursor ion charge state on the formation of product ions. To more fully understand this effect, electrospray ionization coupled to a quadrupole ion trap mass spectrometer, collision-induced dissociation, and gas-phase ion/ion reactions have been employed to examine the fragmentation of the [M + 12H]12+ to [M + H]+ ions of bovine ubiquitin. At low charge states (+1 to +6), loss of NH3 or H2O from the protonated precursor and directed cleavage at aspartic acid residues was observed. At intermediate charge states, (+7, +8, and +9), extensive nonspecific fragmentation of the protein backbone was observed, with 50% sequence coverage obtained from the [M + 8H]8+ ion alone. At high charge states, (+10, +11, +12), the single dominant channel that was observed was the preferential fragmentation of a single proline residue. These data can be readily explained in terms of the current model for intramolecular proton mobilization, that is, the "mobile proton model", the mechanisms for amide bond dissociation developed for protonated peptides, as well as the structures of the multiply charged ions of ubiquitin in the gas phase, examined by ion mobility and hydrogen/deuterium exchange measurements.     

Electron-induced dissociation of singly charged organic cations as a tool for structural characterization of pharmaceutical type molecules

Collision-induced dissociation (CID) and electron-induced dissociation (EID) have been investigated for a selection of small, singly charged organic molecules of pharmaceutical interest. Comparison of these techniques has shown that EID carried out on an FTICR MS and CID performed on a linear ion trap MS produce complementary data. In a study of 33 molecule-cations, EID generated over 300 product ions compared to 190 product ions by CID with an average of only 3 product ions per precursor ion common to both tandem MS techniques. Even multiple stages of CID failed to generate many of the product ions observed following EID. The charge carrying species is also shown to have a very significant effect on the degree of fragmentation and types of product ion resulting from EID. Protonated species behave much like the ammonium adduct with suggestion of a hydrogen atom from the charge carrying species strongly affecting the fragmentation mechanism. Sodium and potassium are retained by nearly every product ion formed from [M + Na](+) or [M + K](+) and provide information to complement the EID of [M + H](+) or [M + NH(4)](+). In summary, EID is proven to be a fitting partner to CID in the structural elucidation of small singly charged ions and by studying EID of a molecule-ion holding different charge carrying species, an even greater depth of detail can be obtained for functional groups commonly used in synthetic chemistry.     

Kinetic Process and Conductivity of Ag~+ Ion Exchange for Polycrystalline Na-β"-Al_2O_3

This paper reports the kinetic process of Ag ion exchange for the polycrystalline Na-β"-Al2O3.The interdiffusion coefficients in the process of Ag+ and Na+ ion exchange have been calculated with an "one dimensional double side diffusion model". Microstructures of the samples were observed and analysed by XRD, EMPA, SEM. The results of the conductivity measurements for samples with Na+, Ag+ and Na+-Ag+ mobile ions are presented and explained     

Action spectroscopy of H3+ and D2H+ using overtone excitation

The H3+ ion and its deuterated isotopologues H2D+, D2H+ and D3+ play an important role in astrophysical and laboratory plasmas. The main challenge for understanding these ions and their interaction at low temperatures are state-specific experiments. This requires manipulation and a simple but efficient in situ characterization of their low-lying rotational states. In this contribution we report measurements of near infrared (NIR) absorption spectra. Required high sensitivity is achieved by combining liquid nitrogen cooled plasma with the technique of NIR cavity ringdown absorption spectroscopy. The measured transition frequencies are then used for exciting cold ions stored in a low-temperature 22-pole radiofrequency ion trap. Absorption of a photon by the stored ion is detected by using the laser-induced reactions technique. As a monitor reaction, the endothermic proton (or deuteron) transfer to Ar is used in our studies. Since the formed ArH+ (or ArD+) ions are detected with near unit efficiency, the stored ions can be characterized very efficiently, even if there are just a few of them.     

Effects of mobile-phase additives, solution pH, ionization constant, and analyte concentration on the sensitivities and electrospray ionization mass spectra of nucleoside antiviral agents

The effects of various mobile-phase additives, solution pH, pKa, and analyte concentration on electrospray ionization mass spectra of a series of purine and pyrimidine nucleoside antiviral agents were studied in both positive and negative ion models. The use of 1% acetic acid resulted in good HPLC separation and the greatest sensitivity for [M + H]+ ions. In the negative ion mode, 50 mM ammonium hydroxide gave the greatest sensitivity for [M - H]- ions. The sensitivities as [M + H]+ ions were significantly larger than the sensitivities as [M - H]- ions for purine antiviral agents. Vidarabine monophosphate and pyrimidine antiviral agents, however, showed comparable or greater sensitivities as [M - H]- ions. The sensitivity as [M + H]+ showed no systematic variation with pH; however, the sensitivity as [M - H]- did increase with increasing pH. At constant pH, the ion intensity of the protonated species increased with increasing pKa. At higher analyte concentrations, dimer (M2H+) and trimer (M3H+) ions were observed. [M + Na]+ adducts were the dominant ions with 0.5 mM sodium salts for these compounds. The spectra of the more basic purine antiviral agents showed no [M + NH4]+ adduct ions, but [M + NH4]+ ions were the major peaks in the spectra of the less basic pyrimidine antiviral agents with ammonium salts. The ammonium adduct ion was formed preferentially when the proton affinity of the analyte was close to that of NH3. Abundant [M + OAc]- ions were observed for all of the antiviral agents except vidarabine monophosphate from solutions with added HOAc, NaOAc, and NH4OAc. The utility of mobile phases containing 1% HOAc or 50 mM NH4OH was demonstrated for chromatographic separations.     

Secondary ion mass spectrometry of zeolite materials: observation of abundant aluminosilicate oligomers using an ion trap

Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)(-)(m+n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (approximately 5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.     

Analysis of VX on soil particles using ion trap secondary ion mass spectrometry.

The direct detection of the nerve agent VX (methylphosphonothioic acid, S-[2-[bis(1-methylethyl)amino]ethyl] O-ethyl ester) on milligram quantities of soil particles has been achieved using ion trap secondary ion mass spectrometry (IT-SIMS). VX is highly adsorptive toward a wide variety of surfaces; this attribute makes detection using gas-phase approaches difficult but renders the compound very amenable to surface detection. An ion trap mass spectrometer, modified to perform SIMS, was employed in the present study. A primary ion beam (ReO4-) was fired on axis through the ion trap, where it impacted the soil particle samples. [VX + H]+, [VX + H]+ fragment ions, and ions from the chemical background were sputtered into the gas-phase environment of the ion trap, where they were either scanned out or isolated and fragmented (MS2). At a surface concentration of 0.4 monolayer, intact [VX + H]+, and its fragment ions, were readily observable above background. However, at lower concentrations, the secondary ion signal from VX became obscured by ions derived from the chemical background on the surface of the soil particles. MS2 analysis using the ion trap was employed to improve detection of lower concentrations of VX: detection of the 34S isotopic ion of [VX + H]+, present at a surface concentration of approximately 0.002 monolayer, was accomplished. The study afforded the opportunity to investigate the fragmentation chemistry of VX. Semiempirical calculations suggest strongly that the molecule is protonated at the N atom. Deuterium labeling showed that formation of the base peak ion (C2H4)N(i-C3H7)2+ involves transfer of the amino proton to the phosphonothioate moiety prior to, or concurrent with, C-S bond cleavage. To manage the risk associated with working with the compound, the vacuum unit of the IT-SIMS was located in a hood, connected by cables to the externally located electronics and computer.     

Secondary ion emission from solutions: time dependence and surface phenomena.

The temporal behavior of FAB mass spectra from glycerol solutions of tetradecyltrimethylammonium bromide (C14H29-N(CH3)3Br, TTAB) and tetraethylammonium iodide (TEAI) was investigated. FAB spectra of the TTAB solution displayed a continuous decrease in TTA+ with time. Spectra obtained from the TEAI solution were initially invariant for several minutes and then displayed a gradual increase in the relative abundance of TEA+ to a maximum, followed by a precipitous drop in ion intensity. Secondary ion images of droplets of TTAB solution showed that emission of both TTA+ and glycerol secondary ions was homogeneous across the sample. Secondary ion images of droplets of TEAI solution showed heterogeneous and segregated emission of both TEA+ and protonated glycerol. Results from the FAB spectra and the secondary ion images were correlated and rationalized on the basis of surface tension-induced mass transport and matrix evaporation.     

Structural, optical and electrical properties of nitrogen ion implanted ZnO nanorods

This study examined the micro-structural and electrical properties of N+-ion-implanted ZnO nanorods. Nitrogen ions with energies of 10-90 keV and beam fluxes of 10(13)-10(16) ions/cm2 were implanted on vertically-aligned ZnO nanorods. Energy dispersive X-ray spectroscopy measurements showed that N+ ions were spread uniformly over the nanorods. Extended X-ray absorption fine structure measurements revealed that the implanted N+s had partially substituted for the oxygen sites. Photoluminescence measurements showed a neutral-donor bound exciton peak at 3.36 eV and a two-electron-satellite peak at 3.33 eV independent of the ion energy and flux. The I-V characteristic curves showed that the current density was not changed by the N+ ion energy and flux much. These results strongly suggested that the N ions substituted for the oxygen sites were neutral.     

Swift heavy ion induced structural,optical and luminescence modification in NaSrBO3:Dy3+ phosphor

The effect of 120 MeVAg⁹⁺ ion irradiation on the structural, optical and luminescence properties of NaSr_1-xBO₃:xDy³⁺ (x = 0.5–2.5 mol%) phosphor synthesized by the conventional solid state reaction route is reported. The samples were irradiated with Ag⁹⁺ swift heavy ions (SHIs) using fluences of 1 × 10¹², 5 × 10¹² and 1 × 10¹³ ions cm^?2. The unirradiated as well as irradiated samples were characterized by powder X-ray diffraction (PXRD), diffuse reflectance (DR) and photoluminescence techniques. PXRD confirms no change in the phase after irradiation except that loss of crystallinity had been observed which may be due to the fragmentation caused by the SHI. A blue shift in the absorption band of the DR was observed, resulting in an increase in the band gap from 5.61 eV to 5.77 eV, after ion irradiation. An increase in photoluminescence intensity (excited at 385 nm) was observed with increased ion fluences. The ratio of the blue to yellow emission peaks (I₄₈₃/I₅₇₇) was calculated and found to be varying with ion fluences suggesting that the white light can be achieved by tailoring this yellow to blue ratio. The Commission Internationale de l’Eclairage coordinates were calculated and found to move toward the white region after irradiation.