Collision-induced state-changing rate coefficients for cyanogen backbones NCN 3Σ- and CNN 3Σ- in astrophysical environments.

We report quantum calculations involving the dynamics of rotational energy-transfer processes, by collision with He atoms in interstellar environments, of the title molecular species which share the presence of the CN backbone and are considered of importance in those environments. The latter structural feature is taken to be especially relevant for prebiotic chemistry and for its possible role in the processing of the heterocyclic rings of RNA and DNA nucleobases in the interstellar space. We carry out ab initio calculations of their interaction potentials with He atoms and further obtain the state-to-state rotationally inelastic cross sections and rate coefficients over the relevant range of temperatures. The similarities and differences between such species and other similar partners which have been already detected are analyzed and discussed for their significance on internal state populations in interstellar space for the two title molecular radicals.

Vibrational Quenching of Optically Pumped Carbon Dimer Anions.

Careful control of quantum states is a gateway to research in many areas of science such as quantum information, quantum-controlled chemistry, and astrophysical processes. Precise optical control of molecular ions remains a challenge due to the scarcity of suitable level schemes, and direct laser cooling has not yet been achieved for either positive or negative molecular ions. Using a cryogenic wire trap, we show how the internal quantum states of C_{2}^{-} anions can be manipulated using optical pumping and inelastic quenching collisions with H_{2} gas. We obtained optical pumping efficiencies of about 96% into the first vibrational level of C_{2}^{-} and determined the absolute inelastic rate coefficient from v=1 to 0 to be k_{q}=(3.2±0.2_{stat}±1.3_{sys})×10^{-13} cm^{3}/s at 20(3) K, over 3 orders of magnitude smaller than the capture limit. Reduced-dimensional quantum scattering calculations yield a small rate coefficient as well, but significantly larger than the experimental value. Using optical pumping and inelastic collisions, we also realized fluorescence imaging of negative molecular ions. Our work demonstrates high control of a cold ensemble of C_{2}^{-}, providing a solid foundation for future work on laser cooling of molecular ions.

The role of small molecular cations in the chemical flow of the interstellar environments.

Molecular ions have been ubiquitous in a variety of environments in the interstellar medium, from Circumstellar Envelopes to Dark Molecular Clouds and to Diffuse Clouds. Their role in the multitude of molecular processes which have been found to occur in those environments has been the subject of many studies over the years, so that we have acquired by now a complex body of data on their chemical structures, their possible function within chemical reactions and their most likely paths to formation. In the present work we review a broad range of such molecular ions, focusing exclusively on positive ions involving the smallest and simplest cations which have been either detected or conjectured as present in the interstellar medium (ISM). We therefore consider mainly molecular cations formed with components like H, H+, He and He+, atomic species which are by far the most abundant baryons in the ISM in general. Their likely structures and their roles in a variety of chemical energy flow paths are discussed and presented within the context of their interstellar environments.

Investigating Possible Dipole-Bound States of Cyanopolyynes: the Case for the C5 N- Anion Detected in Interstellar Space.

We present results of quantum structure calculations aimed at demonstrating the possible existence of dipole-bound states (DBS) for the anion C 5 N - ${{\rm{C}}_5 {\rm{N}}^ - }$ , a species already detected in the Interstellar medium (ISM). The positive demonstration of DBS existence using ab initio studies is an important step toward elucidating possible pathways for the formation of the more tightly bound valence bound states (VBS) in environments where free electrons from starlight ionization processes are known to be available to interact with the radical partner of the title molecule. Our current calculations show that such excited DBS states can exist in C 5 N - ${{\rm{C}}_5 {\rm{N}}^ - }$ , in agreement with what we had previously found for the smallercyanopolyyne in the series: the C 3 N - ${{\rm{C}}_3 {\rm{N}}^ - }$ anion. This system has a very weakly bound anion with binding energies of about 3 and 9 cm-1 for the 1 Σ + ${^1 \Sigma ^ + }$ and 3 Σ + ${^3 \Sigma ^ + }$ DBS, respectively.

Three-Body Collisions Driving the Ion-Molecule Reaction C2- + H2 at Low Temperatures.

We report on the three-body reaction rate of C2- with H2 producing C2H- studied in a cryogenic 16-pole radio frequency ion trap. The reaction was measured in the temperature range from 10 to 28 K, where it was found to only take place via three-body collisions. The experimentally determined termolecular rate coefficient follows the form of a·(T/T0)b with T0 = 20 K, where a = 8.2(3) × 10-30 cm6/s and b = -0.82(12) denotes the temperature dependence. We additionally performed accurate ab initio calculations of the forces between the interacting partners and carried out variational transition state theory calculations, including tunneling through the barrier along the minimum energy path. We show that, while a simple classical model can generally predict the temperature dependence, the variational transition state theoretical calculations, including accurate quantum interactions, can explain the dominance of three-body effects in the molecular reaction mechanism and can reproduce the experimentally determined reaction coefficients, linking them to a temperature-dependent coupling parameter for energy dissipation within the transition complex.

The CH-3Σ+ Anion: Inelastic Rate Coefficients from Collisions with He at Interstellar Conditions.

We present accurate ab initio calculations on several properties of a gas-phase system of interest in the interstellar medium (ISM), where the title molecular anion has been often surmised but not yet confirmed by observations. The CH-3Σ+ constitutes the smallest term in the series of longer anionic polyynes which have been observed in the ISM (e.g., C4H- and several others). Hence, its dynamical behavior in collision with He atoms, one of the most abundant atoms in that environment, can provide quantitative indicators on the changes which can occur in the rotational state population of the title anion when driven by this collision dynamics. We therefore report an accurate evaluation of the full potential energy surface (PES) which acts between the molecular anion in its ground vibrational state and the He atom. The relevant inelastic scattering cross sections and the corresponding inelastic rate coefficients are then computed within a quantum treatment of the collisions. We find that the fairly small values of the final inelastic rate coefficients indicate state-changing processes by collisions to be inefficient paths for modifying the rotational state populations of this anion and therefore to aid its possible observation from direct radiative emission in the microwave region.

Collisional Quantum Dynamics for MgH- (1Σ+) With He as a Buffer Gas: Ionic State-Changing Reactions in Cold Traps.

We present in this paper a detailed theoretical and computational analysis of the quantum inelastic dynamics involving the lower rotational levels of the MgH- (X1Σ+) molecular anion in collision with He atoms which provide the buffer gas in a cold trap. The interaction potential between the molecular partner and the He (1 S) gaseous atoms is obtained from accurate quantum chemical calculations at the post-Hartree-Fock level as described in this paper. The spatial features and the interaction strength of the present potential energy surface (PES) are analyzed in detail and in comparison with similar, earlier results involving the MgH+ (1Σ) cation interacting with He atoms. The quantum, multichannel dynamics is then carried out using the newly obtained PES and the final inelastic rats constants, over the range of temperatures which are expected to be present in a cold ion trap experiment, are obtained to generate the multichannel kinetics of population changes observed for the molecular ion during the collisional cooling process. The rotational populations finally achieved at specific temperatures are linked to state-selective laser photo-detachment experiments to be carried out in our laboratory.All intermediate steps of the quantum modeling are also compared with the behavior of the corresponding MgH+ cation in the trap and the marked differences which exist between the collisional dynamics of the two systems are dicussed and explained. The feasibility of the present anion to be involved in state-selective photo-detachment experiments is fully analyzed and suggestions are made for the best performing conditions to be selected during trap experiments.

Collisional relaxation kinetics for ortho and para NH2- under photodetachment in cold ion traps.

The collisional cooling of the internal rotational states of the nonlinear anion NH2- (1A1), occurring at the low temperature of a cold ion trap under helium buffer gas cooling, is examined via quantum dynamics calculations and ion decay rate measurements. The calculations employ a novel ab initio potential energy surface that describes the interaction anisotropy and range of action between the molecular anions and the neutral He atoms. The state changing integral cross sections are employed to obtain the state-to-state rate coefficients, separately for the ortho- and the para-NH2- ions. These rates are in turn used to compute the state population evolution in the trap for both species, once photodetachment by a laser is initiated in the trap. The present work shows results for the combined losses of both species after the photodetachment laser is switched on and analyzes the differences of loss kinetics between the two hyperfine isomers.

Isomeric Broadening of C60+ Electronic Excitation in Helium Droplets: Experiments Meet Theory.

Helium is considered an almost ideal tagging atom for cold messenger spectroscopy experiments. Although helium is bound very weakly to the ionic molecule of interest, helium tags can lead to shifts and broadenings that we recorded near 963.5 nm in the electronic excitation spectrum of C60+ solvated with up to 100 helium atoms. Dedicated quantum calculations indicate that the inhomogeneous broadening is due to different binding energies of helium to the pentagonal and hexagonal faces of C60+, their dependence on the electronic state, and the numerous isomeric structures that become available for intermediate coverage. Similar isomeric effects can be expected for optical spectra of most larger molecules surrounded by nonabsorbing weakly bound solvent molecules, a situation encountered in many messenger-tagging spectroscopy experiments.

Chemical solutions in a quantum solvent: anionic electrolytes in 4He nanodroplets.

Variational and diffusion Monte Carlo (VMC and DMC) calculations are presented for anionic electrolytes solvated in (4)He. The electrolytes have the general structure X(-)(He)(N), with X=F, Cl, Br and I, and N varying up to 40 (41 for I(-)). The overall interaction potential is obtained from accurate ab initio data for the two-body components and then using the sum-of-potentials approximation. Our computational scheme is a robust procedure, giving us accurate trial wavefunctions that can be used to perform high-quality DMC calculations. The results indicate very marked delocalization and permanence of the liquid-like quantum features of the solvent adatoms surrounding the anionic impurities. This finding stands in contrast to the more structured, solid-like behavior of the quantum solutions with alkali metal cations embedded in He nanodroplets. While other negatively charged species such as H(-) have shown an overall repulsive interaction with He, the present calculations clearly indicate that the halogen anions remain solvated within liquid-like solvent "bubbles" of species-dependent size.

Rovibrational structures in floppy triatomics: distributed gaussian functions treatment for the Ne2H- system.

The full sequence of the bound states for a very floppy triatomic complex, Ne2H- in its ground electronic state, are initially computed for the rotationless situation and employing a variational approach that expands the total nuclear wave function over a large set of symmetry-adapted, distributed Gaussian functions and employs accurate atom-atom potential energy data. The results are tested for numerical convergence, compared with the behavior of both its diatomic fragments, Ne2 and NeH-, and further compared with the results for the Ne3 case. The computational analysis is extended to the production of the rotational constants for the very nonclassical ground state vibrational configuration by making use of the previous findings. The method is shown to provide us with several illuminating details on the nanoscopic internal dynamics of this very weakly bound quantum aggregate.