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The anions C$_7$N$^-$ and C$_{10}$H$^-$ are the two longest of the linear (C,N)-bearing and (C,H)-bearing chains which have so far been detected in the Interstellar Medium. In order to glean information on their collision-induced rotational state-changing processes, we analyse the general features of new ab initio potentials describing the interaction of both linear anions with H$_2$, one of the most abundant partners in their ISM environment. We employ an artificial neural network fit of the reduced-dimensionality potential energy surface for C$_7$N$^-$...H$_2$ interaction and discuss in detail the spatial features in terms of multipolar radial coefficients. For the C$_{10}$H$^-$...H$_2$ interaction we use the initial grid of two dimensional raw points to generate by quadrature the Legendre expansion directly, further including the long-range terms as discussed in the main text. Quantum scattering calculations are employed to obtain rotationally inelastic cross sections, for collision energies in the range of 10$^{-4}$ to 400 cm$^{-1}$. From them we generate the corresponding inelastic rate coefficients as a function of temperature covering the range from 10 to 50 K. The results for the rate coefficients for the longest cyanopolyyne are compared with the earlier results obtained for the smaller terms of the same series, also in collision with H$_2$. We obtain that the inelastic rate coefficients for the long linear anions are all fairly large compared with the earlier systems. The consequences of such findings on their non-equilibrium rotational populations in interstellar environments are illustrated in our conclusions.

We report new results from quantum calculations of energy-transfer processes taking place in interstellar environments and involving two newly observed molecular species: C$_5$N$^-$ and C$_7$N$^-$ in collision with He atoms and the p-H$_2$ molecules. These species are part of the anionic molecular chains labeled as cyanopolyynes which have been observed over the years in molecule-rich Circumstellar Envelopes and in molecular clouds. In the present work, we first carry out new $ab$ $initio$ calculations for the C$_7$N$^-$ interaction potential with He atom and then obtain state-to-state rotationally inelastic cross sections and rate coefficients involving the same transitions which have been observed experimentally by emission in the interstellar medium (ISM) from both of these linear species. For the C$_5$N$^-$/He system we extend the calculations already published in our earlier work (see reference below) to compare more directly the two molecular anions. We extend further the quantum calculations by also computing in this work collision rate coefficients for the hydrogen molecule interacting with C5N$^-$, using our previously computed interaction potential. Additionally, we obtain the same rate coefficients for the C$_7$N$^-$/H$_2$ system by using a scaling procedure that makes use of the new C$_7$N$^-$/He rate coefficients, as discussed in detail in the present paper. Their significance in affecting internal state populations in ISM environments where the title anions have been found is analyzed by using the concept of critical density indicators. Finally, similarities and differences between such species and the comparative efficiency of their collision rate coefficients are discussed. These new calculations suggest that, at least for the case of these longer chains, the rotational populations could reach local thermal equilibrium conditions within their observational environments.

We present in this paper the main structural features and enthalpy details for the energy profiles of the title reactions, both for the exothermic (forward) path to NH$_{3}$ formation and for the endothermic (reverse) reaction to NH$_{2}^{-}$ formation. Both systems have relevance for the nitrogen chemistry in the interstellar medium (ISM). They are also helpful to document the possible role of H$^{-}$ in molecular clouds at temperatures well below room temperature. The structural calculations are carried out using ab initio methods and are further employed to obtain the reaction rates down to the interstellar temperatures detected in earlier experiments. The reaction rates are obtained from the computed Minimum Energy Path (MEP) using the Variational Transition State Theory (VTST) approach. The results indicate very good accord with the experiments at room temperature, while the measured low temperature data down to 8 K are well described once we analyse in detail the physics of the reactions and modify accordingly the VTST approach. This is done by employing a T-dependent scaling, from room temperature conditions down to the lower ISM temperatures, which acknowledges the non-canonical behavior of the fast, barrierless exothermic reaction. This feature was also suggested in the earlier work discussed below in our main text. The physical reasons for the experimental behavior, and the need for improving on the VTST method when used away from room temperatures, are discussed in detail.

Using the ab initio computed Potential Energy Surface (PES) for the electronic interaction of the MgH$^+$ ($^1\Sigma$) ion with the He($^1$S) atom, we calculate the relevant state-changing rotationally inelastic collision cross sections from a quantum treatment of the multichannel scattering problem. We focus on the quantum dynamics at the translationally low energies for the present partners discussed in the earlier, cold ion trap experiments (see below) which we wish to model in detail. The corresponding state-changing rates computed between the lower rotational states of the molecular ion are employed to describe the time-evolution kinetics followed by recent experiments on Coulomb-crystalized MgH$^+$ ($^1\Sigma$), where the ions are rotationally cooled by micromotion tuning after the uploading into the trap of He as a buffer gas. The present computational modeling of the final ions' rotational temperatures in the experiments turns out to agree very well with their observations and points at a fast equilibration between rotational and thermal temperatures of the ions.

We employ an accurate, ab initio potential energy surface (PES) which describes the electronic interaction energy between the molecular anion OH$^-$ ($^1\Sigma^+$) and the neutral rubidium atom Rb ($^2S$), to evaluate the elastic and inelastic cross sections over a range of energies representative of the conditions of low-T experiments in MOT traps, when combined with laser-cooled rubidium gas. The system is considered to be in its vibrational ground state, while the first four rotational levels are taken to be involved in the cooling and heating collisional processes that are computed here. The corresponding cooling and heating rates up to about 35 K are obtained from the calculations and compared with the recent results in a similar experiments, where He was the partner atom of the current anion.

This paper deals with the possible formation of two molecular anions often considered likely components in the physical environments of the Interstellar Medium ( ISM) : $\mathrm{C_2H^-}$ and $\mathrm{NCO^-}$. They are both discussed here by computationally following the radiative association (RA) mechanism starting from $\mathrm{C_2^-}$, $\mathrm{H}$, $\mathrm{NC^-}$ and $\mathrm{O}$ as partners. The corresponding RA total cross sections produced by the calculations are in turn employed to generate the overall association rates over the relevant range of temperatures. The latter are found to be in line with other molecular ions formed by RA but not large enough to uniquivocally suggest this path as the main route to the anions formation in the ISM. Other possible paths of formation are also analysed and discussed. The presence of resonant structures during the association dynamics for both systems is found by the calculations and their consequences are discussed in some detail in the present study.

We investigate the relative efficiencies of low-temperature chemical reactions in the Interstellar medium (ISM) with H$^-$ anion reacting in the gas phase with cyanopolyyne neutral molecules, leading to the formation of anionic C$_x$N$^-$ linear chains of different length and of H$_2$. All the reactions turn out to be without barriers, highly exothermic reactions which provide a chemical route to the formation of anionic chains of the same length . Some of the anions have been observed in the dark molecular clouds and in the diffuse interstellar envelopes.Quantum calculations are carried for the corresponding reactive potential energy surfaces (RPESs) for all the odd-numbered members of the series (x=1, 3, 5, 7). We employ the Minimum Energy paths (MEPs) to obtain the relevant Transition State (TS) configurations and use the latter within the Variational Transition State ( VTS) model to obtain the chemical rates. The present results indicate that, at typical temperatures around 100 K, a set of significantly larger rate values exists for x=3 and x=5, while are smaller for CN$^-$ and C$_7$N$^-$. At those temperatures, however, all the rates turn out to be larger than the estimates in the current literature for the Radiative Electron Attachment (REA) rates, thus indicating the greater importance of the present chemical path with respect to REA processes at those temperatures. The physical reasons for our findings are discussed in detail and linked with the existing observational findings.

In the present paper we analyze in detail several properties of the MgH$^-$ anion and the MgH neutral molecule using accurate ab initio quantum computational methods in order to establish with higher reliability specific molecular features like the gas-phase electron affinity (EA) , the Frank-Condon (FC) factors for excitation of the neutral and of its anion to their lower electronic states, and the general feasibility of employing the anion in photodetachment experiments after its confinement in cold ion traps. The calculations suggest that the EA value is in agreement with an existing early experiment and further places on it a smaller error bar than that given before. Accurate zero-point-energy (ZPE) corrections are also included in our calculations and their effects discussed.

We construct the velocity map images of the proton transfer reaction between helium and molecular hydrogen ions H2+. We perform simulations of imaging experiments at one representative total collision energy taking into account the inherent aberrations of the velocity mapping in order to explore the feasibility of direct comparisons between theory and future experiments planned in our laboratory. The asymptotic angular distributions of the fragments in a 3D velocity space is determined from the quantum state-to-state differential reactive cross sections and reaction probabilities which are computed by using the time-independent coupled channel hyperspherical coordinate method. The calculations employ an earlier ab initio potential energy surface computed at the FCI/cc-pVQZ level of theory. The present simulations indicate that the planned experiments would be selective enough to differentiate between product distributions resulting from different initial internal states of the reactants.

Cryogenic 22-pole ion traps have found many applications in ion-molecule reaction kinetics and in high resolution molecular spectroscopy. For most of these applications it is important to know the translational and internal temperatures of the trapped ions. Here, we present detailed rotational state thermometry measurements over an extended temperature range for the two ion/buffer gas systems OH-/He and OD-/HD with ion-to-neutral mass ratios of 4.25 and 6 respectively. The measured rotational temperatures show a termination of the thermalisation with the buffer gas around 25K, independent of mass ratio and confinement potential of the trap. Different possible explanations for this incomplete thermalisation have been investigated, among them the thermalisation of the buffer gas and the heating due to room temperature blackbody radiation and room temperature gas entering the trap.

(abridged) The fairly recent detection of a variety of anions in the Interstellar Molecular Clouds have underlined the importance of realistically modeling the processes governing their abundance. To this aim, our earlier calculations for the radiative electron attachment (REA) rates for C4H-, C6H-, and C8H- are employed to generate the corresponding column density ratios of anion/neutral (A/N) relative abundances. The latter are then compared with those obtained from observational measurements. The calculations involved the time-dependent solutions of a large network of chemical processes over an extended time interval and included a series of runs in which the values of REA rates were repeatedly scaled. Macroscopic parameters for the clouds' modeling were also varied to cover a broad range of physical environments. It was found that, within the range and quality of the processes included in the present network,and selected from state-of-the-art astrophysical databases, the REA values required to match the observed A/N ratios needed to be reduced by orders of magnitude for C4H- case, while the same rates for C6H- and C8H- only needed to be scaled by much smaller factors. The results suggest that the generally proposed formation of interstellar anions by REA mechanism is overestimated by current models for the C4H- case, for which is likely to be an inefficient path to formation. This path is thus providing a rather marginal contribution to the observed abundances of C4H-, the latter being more likely to originate from other chemical processes in the network, as we discuss in some detail in the present work.Possible physical reasons for the much smaller differences against observations found instead for the values of the (A/N) ratios in two other, longer members of the series are put forward and analyzed within the evolutionary modeling discussed in the present work., Comment: Journal of Physics B, accepted

We are developing a new hybrid atom-ion trap to study the interaction of ultracold rubidium atoms with mass-selected OH- molecules. The ions are trapped inside an octupole rf-trap made of thin wires instead of the commonly used rods. This ensures good optical access to the center of the trap where the ions can be overlapped with laser cooled rubidium atoms stored in a dark spontaneous force optical trap (dark SPOT). This setup provides high collision rates since the density in a dark SPOT is about one order of magnitude higher than in a standard magneto-optical trap. Further, inelastic collisions with excited atoms are suppressed since almost all atoms are in the ground state. Numerical simulations of our setup using SIMION predict that cooling of the ions is feasible.

Chemical models used to study the chemical composition of the gas and the ices in the interstellar medium are based on a network of chemical reactions and associated rate coefficients. These reactions and rate coefficients are partially compiled from data in the literature, when available. We present in this paper kida.uva.2014, a new updated version of the kida.uva public gas-phase network first released in 2012. In addition to a description of the many specific updates, we illustrate changes in the predicted abundances of molecules for cold dense cloud conditions as compared with the results of the previous version of our network, kida.uva.2011., Comment: Accepted for publication in ApJS on February 26th, 2015

Photodetachment spectroscopy of OH- and H3O2- anions has been performed in a cryogenic 22-pole radiofrequency multipole trap. Measurements of the detachment cross section as a function of laser frequency near threshold have been analysed. Using this bound-free spectroscopy approach we could demonstrate rotational and vibrational cooling of the trapped anions by the buffer gas in the multipole trap. Below 50 K the OH- rotational temperature shows deviations from the buffer gas temperature, and possible causes for this are discussed. For H3O2- vibrational cooling of the lowest vibrational quantum states into the vibrational ground state is observed. Its photodetachment cross section near threshold is modelled with a Franck-Condon model, with a detachment threshold that is lower, but still in agreement with the expected threshold for this system.

Absolute photodetachment cross sections of two anions of astrophysical importance CN- and C3N- were measured to be (1.18 +- (0.03)_stat (0.17)_sys) * 10^-17 cm^2 and (1.43 +- (0.14)_stat (0.37)_sys) * 10^-17 cm^2 respectively at the ultraviolet wavelength of 266 nm (4.66 eV). These relatively large values of the cross sections imply that photodetachment can play a major role in the destruction mechanisms of these anions particularly in photon-dominated regions. We have therefore carried out model calculations using the newly measured cross sections to investigate the abundance of these molecular anions in the cirumstellar envelope of the carbon-rich star IRC+10216. The model predicts the relative importance of the various mechanisms of formation and destruction of these species in different regions of the envelope. UV photodetachment was found to be the major destruction mechanism for both CN- and C3N- anions in those regions of the envelope, where they occur in peak abundance. It was also found that photodetachment plays a crucial role in the degradation of these anions throughout the circumstellar envelope.

The charge transfer reaction Ar+ + N2 --> Ar + N2+ has been investigated in a crossed beam experiment in combination with three-dimensional velocity map imaging. Angular differential state-to-state cross sections were determined as a function of the collision energy. We found that scattering into the first excited vibrational level dominates as expected, but only for scattering in the forward direction. Higher vibrational excitations up to v'=6 have been observed for larger scattering angles. For decreasing collision energy, scattering into higher scattering angles becomes increasingly important for all kinematically allowed quantum states. Our detailed measurements indicate that a quantitative agreement between experiment and theory for this basic ion-molecule reaction now comes within reach., Comment: accepted to Phys. Rev. Lett

We present a novel chemical database for gas-phase astrochemistry. Named the KInetic Database for Astrochemistry (KIDA), this database consists of gas-phase reactions with rate coefficients and uncertainties that will be vetted to the greatest extent possible. Submissions of measured and calculated rate coefficients are welcome, and will be studied by experts before inclusion into the database. Besides providing kinetic information for the interstellar medium, KIDA is planned to contain such data for planetary atmospheres and for circumstellar envelopes. Each year, a subset of the reactions in the database (kida.uva) will be provided as a network for the simulation of the chemistry of dense interstellar clouds with temperatures between 10 K and 300 K. We also provide a code, named Nahoon, to study the time-dependent gas-phase chemistry of 0D and 1D interstellar sources., Comment: Accepted for publication in ApJS

We investigate the rovibrational population redistribution of polar molecules in the electronic ground state induced by spontaneous emission and blackbody radiation. As a model system we use optically trapped LiCs molecules formed by photoassociation in an ultracold two-species gas. The population dynamics of vibrational and rotational states is modeled using an ab-initio electric dipole moment function and experimental potential energy curves. Comparison with the evolution of the v"=3 electronic ground state yields good qualitative agreement. The analysis provides important input to assess applications of ultracold LiCs molecules in quantum simulation and ultracold chemistry., Comment: 6 pages, 5 figures, EPJD Topical issue on Cold Quantum Matter - Achievements and Prospects

Recently we demonstrated the formation of ultracold polar LiCs molecules in deeply bound levels of the X1S+ ground state, including the rovibrational ground state [J. Deiglmayr et al., Phys. Rev. Lett. 101, 133004 (2008)]. Here we report on the first experimental determination of the permanent electric dipole moment of deeply bound LiCs molecules. For X1S+,v"=2 and v"=3 we measure values of mu=5.5(2) Debye and 5.3(2) Debye respectively., Comment: 4 pages, 2 figures

We analyse the formation of ultracold 7Li133Cs molecules in the rovibrational ground state through photoassociation into the B1Pi state, which has recently been reported [J. Deiglmayr et al., Phys. Rev. Lett. 101, 133004 (2008)]. Absolute rate constants for photoassociation at large detunings from the atomic asymptote are determined and are found to be surprisingly large. The photoassociation process is modeled using a full coupled-channel calculation for the continuum state, taking all relevant hyperfine states into account. The enhancement of the photoassociation rate is found to be caused by an `echo' of the triplet component in the singlet component of the scattering wave function at the inner turning point of the lowest triplet a3Sigma+ potential. This perturbation can be ascribed to the existence of a broad Feshbach resonance at low scattering energies. Our results elucidate the important role of couplings in the scattering wave function for the formation of deeply bound ground state molecules via photoassociation., Comment: Added Erratum, 20 pages, 9 figures

The column density distribution of trapped OH$^-$ ions in a 22-pole ion trap is measured for different trap parameters. The density is obtained from position-dependent photodetachment rate measurements. Overall, agreement is found with the effective potential of an ideal 22-pole. However, in addition we observe 10 distinct minima in the trapping potential, which indicate a breaking of the 22-fold symmetry. Numerical simulations show that a displacement of a subset of the radiofrequency electrodes can serve as an explanation for this symmetry breaking.

We recently reported the formation of ultracold LiCs molecules in the rovibrational ground state X1Sigma+,v''=0,J''=0 [J. Deiglmayr et al., PRL 101, 133004 (2008)]. Here we discuss details of the experimental setup and present a thorough analysis of the photoassociation step including the photoassociation line shape. We predict the distribution of produced ground state molecules using accurate potential nergy curves combined with an ab-initio dipole transition moment and compare this prediction with experimental ionization spectra. Additionally we improve the value of the dissociation energy for the X1Sigma+ state by high resolution spectroscopy of the vibrational ground state., Comment: Submitted to Faraday Discussions 142: Cold and Ultracold Molecules 18 pages, 8 figures

Ultracold LiCs molecules in the absolute ground state X$^1\Sigma^+$, v"=0, J"=0 are formed via a single photo-association step starting from laser-cooled atoms. The selective production of v"=0, J"=2 molecules with a 50-fold higher rate is also demonstrated. The rotational and vibrational state of the ground state molecules is determined in a setup combining depletion spectroscopy with resonant-enhanced multi-photon ionization time-of-flight spectroscopy. Using the determined production rate of up to 5x10^3 molecules/s, we describe a simple scheme which can provide large samples of externally and internally cold dipolar molecules.

We report on the realisation of a chip-based multipole ion trap manufactured using micro-electromechanical systems (MEMS) technology. It provides ion confinement in an almost field-free volume between two planes of radiofrequency electrodes, deposited on glass substrates, which allows for optical access to the trap. An analytical model of the effective trapping potential is presented and compared with numerical calculations. Stable trapping of argon ions is achieved and a lifetime of 16s is measured. Electrostatic charging of the chip surfaces is studied and found to agree with a numerical estimate.

We identify plain evaporation of ions as the fundamental loss mechanism out of a multipole ion trap. Using thermalized negative Cl- ions we find that the evaporative loss rate is proportional to a Boltzmann factor. This thermodynamic description sheds new light on the dynamics of particles in time-varying confining potentials. It specifically allows us to extract the effective depth of the ion trap as the activation energy for evaporation. As a function of the rf amplitude we find two distinct regimes related to the stability of motion of the trapped ions. For low amplitudes the entire trap allows for stable motion and the trap depth increases with the rf field. For larger rf amplitudes, however, rapid energy transfer from the field to the ion motion can occur at large trap radii, which leads to a reduction of the effective trapping volume. In this regime the trap depth decreases again with increasing rf amplitude. We give an analytical parameterization of the trap depth for various multipole traps that allows predictions of the most favorable trapping conditions., Comment: Phys. Rev. Lett., in press

The absolute photodetachment cross section of OH- anions at a rotational and translational temperature of 170K is determined by measuring the detachment-induced decay rate of the anions in a multipole radio-frequency ion trap. In comparison with previous results, the obtained cross section shows the importance of the initial rotational state distribution. Using a tomography scan of the photodetachment laser through the trapped ion cloud, the derived cross section is model-independent and thus features a small systematic uncertainty. The tomography also yields the column density of the OH- anions in the 22-pole ion trap in good agreement with the expected trapping potential of a large field free region bound by steep potential walls., Comment: Phys. Rev. Lett., in press

We present studies of strong coupling in single-photon photoassociation of cesium dimers using an optical dipole trap. A thermodynamic model of the trap depletion dynamics is employed to extract absolute rate coefficents. From the dependence of the rate coefficient on the photoassociation laser intensity, we observe saturation of the photoassociation scattering probability at the unitarity limit in quantitative agreement with the theoretical model by Bohn and Julienne [Phys. Rev. A, 60, 414 (1999)]. Also the corresponding power broadening of the resonance width is measured. We could not observe an intensity dependent light shift in contrast to findings for lithium and rubidium, which is attributed to the absence of a p or d-wave shape resonance in cesium.

We present quantitative measurements of the photoassociation of cesium molecules inside a far-detuned optical dipole trap. A model of the trap depletion dynamics is derived which allows to extract absolute photoassociation rate coefficients for the initial single-photon photoassociation step from measured trap-loss spectra. The sensitivity of this approach is demonstrated by measuring the Franck-Condon modulation of the weak photoassociation transitions into the low vibrational levels of the outer well of the 0g- state that correlates to the 6s+6p3/2 asymptote. The measurements are compared to theoretical predictions. In a magneto-optical trap these transitions have previously only been observed indirectly through ionization of ground state molecules.