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.     

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.     

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.     

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.     

Ion-pair formation in electron recombination with H3+

The process of resonant ion-pair formation following electron collisions with H3+ is studied. The relevant diabatic potential energy surfaces and the electronic couplings between these surfaces are calculated. The reaction is then described using a time-dependent approach with wave packets propagating on the coupled potentials. In order to describe the reaction, it is found necessary to include at least two dimensions in the model. The effects of the Rydberg states on the cross-section for this process are discussed.     

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+.     

The role of asymptotic vibrational states in H3+

Calculations are discussed which characterize all the vibrational bound states of the H3+ and D2H+ molecular ions using a realistic ab initio potential energy surface. Graphical analysis and calculation of rotational constants show that both ions support a series of atom-diatom-like long-range states: asymptotic vibrational states. The role of these states in the H3+ system and other molecules is discussed. The vibrational calculations are extended above dissociation where the resulting (Feshbach) resonances are shown to be too short-lived to be of importance for the H3+ photodissociation spectrum.     

H3+: the driver of giant planet atmospheres

We present a review of recent developments in the use of H3+ molecular ion as a probe of physics and chemistry of the upper atmospheres of giant planets. This ion is shown to be a good tracer of energy inputs into Jupiter (J), Saturn (S) and Uranus (U). It also acts as a 'thermostat', offsetting increases in the energy inputs owing to particle precipitation via cooling to space (J and U). Computer models have established that H3+ is also the main contributor to ionospheric conductivity. The coupling of electric and magnetic fields in the auroral polar regions leads to ion winds, which, in turn, drive neutral circulation systems (J and S). These latter two effects, dependent on H3+, also result in very large heating terms, approximately 5 x 10(12) W for Saturn and greater than 10(14) W for Jupiter, planet-wide; these terms compare with approximately 2.5 x 10(11) W of solar extreme UV absorbed at Saturn and 10(12) W at Jupiter. Thus, H3+ is shown to play a major role in explaining why the temperatures of the giant planets are much greater (by hundreds of kelvin) at the top of the atmosphere than solar inputs alone can account for.     

Rotation-vibrational states of H3+ and the adiabatic approximation

We discuss recent progress in the calculation and identification of rotation-vibrational states of H3+ at intermediate energies up to 13,000 cm(-1). Our calculations are based on the potential energy surface of Cencek et al. which is of sub-microhartree accuracy. As this surface includes diagonal adiabatic and relativistic corrections to the fixed nuclei electronic energies, the remaining discrepancies between our calculated and experimental data should be due to the neglect of non-adiabatic coupling to excited electronic states in the calculations. To account for this, our calculated energy values were adjusted empirically by a simple correction formula. Based on our understanding of the adiabatic approximation, we suggest two new approaches to account for the off-diagonal adiabatic correction, which should work; however, they have not been tested yet for H3+. Theoretical predictions made for the above-barrier energy region of recent experimental interest are accurate to 0.35 cm(-1) or better.     

Phase equilibrium and PVT-properties of 0.7223H2O + 0.1242 n-C6 H14 + 0.1535 n-C3H7OH ternary system

The results are given of experimental investigation of the PVT-properties and liquid-liquid and liquid-vapor phase equilibria of 0.7223H₂O + 0.1242 n-C₆ H₁₄ + 0.1535 n-C₃H₇OH ternary system along six different isochores. The measurements are performed by the constant-volume piezometer technique in the range of temperature from 309.26 to 678.82 K, density from 81.0 to 485.0 kg/m³, and pressure up to 60 MPa. The behavior of the system in the vicinity of the liquid-liquid and liquid-vapor critical points is treated using the scaling equations. The PVT-properties are described by the Peng-Robinson equation.Translated from Teplofizika Vysokikh Temperatur, Vol. 43, No. 1, 2005, pp. 045–050. Original Russian Text Copyright © 2005 by S. M. Rasulov and A. R. Rasulov.     

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.     

Reaction of Ge with NH3 + H2O Vapor

A formal rate equation is derived for the asymptotic growth of a vaporizing scale, which adequately describes the growth of a nitride layer on germanium in humid ammonia.     

Observations and models of deuterated H3+ in proto-planetary disks

Young, gas-rich proto-planetary disks orbiting around solar-type young stars represent a crucial phase in disk evolution and planetary formation. Of particular relevance is to observationally track the evolution of the gas, which governs the overall evolution of the disk and is eventually dispersed. However, the bulk of the mass resides in the plane, which is so cold and dense that virtually all heavy-element-bearing molecules freeze out onto the dust grains and disappear from the gas phase. In this paper, we show that the ground-state ortho-H2D+ transition is the best, if not the only, tracer of the disk-plane gas. We report the theoretical models of the chemical structure of the plane of the disk, where the deuterated forms of H3+, including H2D+, play a major role. We also compare the theoretical predictions with the observations obtained towards the disk of the young star DM Tau and show that the ionization rate is probably enhanced there, perhaps owing to the penetration of X-rays from the central object through the disk plane. We conclude by remarking that the ground-state ortho-H2D+ transition is such a powerful diagnostic that it may also reveal the matter in the dark halos of external galaxies, if it is hidden in cold, dense and small clouds, as several theories predict.     

Near-infrared spectroscopy of H3+ above the barrier to linearity

Since the Royal Society Discussion Meeting on H3+ in 2000, the laboratory spectroscopy of H3+ has entered a new regime. For the first time, transitions of H3+ above the barrier to linearity have been observed. A highly sensitive near-infrared spectrometer based on a titanium:sapphire laser and incorporating a dual-beam, double-modulation technique with bidirectional optical multi-passing has been developed in order to detect these transitions, which are more than 4600 times weaker than the fundamental band. We discuss our recent work on the 2v1 + 2v2(2) <-- 0, 3v1 + v2(1) <-- 0, v1 + 4v2(2) <-- 0, v1 + 4V2(4) <-- 0 and 2v1 + 3v2(1) <-- 0 combination bands and the 5v2(1) <-- 0, 5v2(3) <-- 0, 52(5) <-- 0 and 6v2(2) <-- 0 overtone bands. Experimentally determined energy levels provide a critical test of ab initio calculations in this challenging energy regime (greater than 10,000 cm(-1)). By comparing the experimental energy levels and theoretical energy levels from ab initio calculations in which the adiabatic and relativistic corrections are incorporated, the extent of higher-order effects such as non-adiabatic and radiative corrections is revealed.     

Dissociative recombination of cold H3+ and its interstellar implications

H3+ plays a key role in interstellar chemistry as the initiator of ion-molecule chemistry. The amount of H3+ observed in dense interstellar clouds is consistent with expectations, but the large abundance of H3+ seen in diffuse clouds is not easily explained by simple chemical models. A crucial parameter in predicting the abundance of H3+ in diffuse clouds is the rate constant for dissociative recombination (DR) with electrons. The value of this constant has been very controversial, because different experimental techniques have yielded very different results, perhaps owing to varying degrees of rotational and vibrational excitation of the H3+ ions. If the value of this rate constant under interstellar conditions were much lower than usually assumed, the large H3+ abundance could be easily explained. In an attempt to pin down this crucial rate constant, we have performed DR measurements at the CRYRING ion storage ring in Stockholm, using a supersonic expansion ion source to produce rotationally cold H3+ ions. These measurements suggest that the DR rate constant in diffuse clouds is not much lower than usually assumed and that the abundant H3+ must be due to either a low electron fraction or a high ionization rate.     

Effects of molecular rotation in low-energy electron collisions of H3+

Measurements on the energetic structure of the dissociative recombination rate coefficient in the millielectronvolt range are described for H3+ ions produced in the lowest rotational levels by collisional cooling and stored as a fast beam in the magnetic storage ring TSR (Test Storage Ring). The observed resonant structure is consistent with that found previously at the storage ring facility CRYRING in Stockholm, Sweden; theoretical predictions yield good agreement on the overall size of the rate coefficient, but do not reproduce the detailed structure. First studies on the nuclear spin symmetry influencing the lowest level populations show a small effect different from the theoretical predictions. Heating processes in the residual gas and by collisions with energetic electrons, as well as cooling owing to interaction with cold electrons, were observed in long-time storage experiments, using the low-energy dissociative recombination rate coefficient as a probe, and their consistency with the recent cold H3+ measurements is discussed.     

H3+ in the electronic triplet state: current status

We review the theoretical work carried out on the tri-hydrogen ion in the electronic triplet state 1(3)E', which is split into a3Sigma+u and 2(3)A' by vibronic interaction. We begin with an overview on analytical potential energy surfaces and calculations of rovibrational states by focusing on our own results, which are based on the most accurate potential energy surfaces available so far. This is followed by an examination of the selection rules and predictions of infrared transition frequencies. Finally, we discuss the Slonczewski resonance states supported by the upper sheet of the potential energy surface. Theoretical work reported here may be of interest for future experiments on the title ion.     

Cl-和H+对2024-T3铝合金初期腐蚀的协同效应

利用电化学工作站、光学显微镜和扫描电镜等设备,测量并观察了2024-T3铝合金在不同 Cl-和 H+浓度水溶液中的极化曲线、开路电位及微观腐蚀形貌;建立了用于双因素协同效应分析的数学模型,量化了 Cl-浓度和 H+浓度对铝合金初期腐蚀速率的主效应、协同效应以及简单效应,探讨了二者的协同作用机制.结果表明:Cl-和 H+浓度增加,铝合金腐蚀加剧,但表观腐蚀形貌未改变;置信度为0.005时,Cl-和 H+浓度对腐蚀速率的主效应及协同效应显著,由主到次可排序为 H+、Cl-、H+×Cl-(协同效应),二者的简单效应亦有显著性差异;二者通过改变钝化膜性质来影响铝合金初期的腐蚀行为,在不同浓度水平下,主导钝化膜破坏的反应有所不同,当H+浓度较高时,钝化膜的溶解破坏占据主导地位,当H+浓度较低时,Cl-和H+对钝化膜的协同破坏占据主导地位.