Scattering matrix approach to the dissociative recombination of HCO+ and N2H+.

We present a theoretical study of the indirect dissociative recombination of linear polyatomic ions at low collisional energies. The approach is based on the computation of the scattering matrix just above the ionization threshold and enables the explicit determination of all diabatic electronic couplings responsible for dissociative recombination. In addition, we use the multi-channel quantum-defect theory to demonstrate the precision of the scattering matrix by reproducing accurately ab initio Rydberg state energies of the neutral molecule. We consider the molecular ions N2H(+) and HCO(+) as benchmark systems of astrophysical interest and improve former theoretical studies, which had repeatedly produced smaller cross sections than experimentally measured. Specifically, we demonstrate the crucial role of the previously overlooked stretching modes for linear polyatomic ions with large permanent dipole moment. The theoretical cross sections for both ions agree well with experimental data over a wide energy range. Finally, we consider the potential role of the HOC(+) isomer in the experimental cross sections of HCO(+) at energies below 10 meV.

Potential energy and dipole moment surfaces of HCO- for the search of H- in the interstellar medium.

Potential energy and permanent dipole moment surfaces of the electronic ground state of formyl negative ion HCO(-) are determined for a large number of geometries using the coupled-cluster theory with single and double and perturbative treatment of triple excitations ab initio method with a large basis set. The obtained data are used to construct interpolated surfaces, which are extended analytically to the region of large separations between CO and H(-) with the multipole expansion approach. We have calculated the energy of the lowest rovibrational levels of HCO(-) that should guide the spectroscopic characterization of HCO(-) in laboratory experiments. The study can also help to detect HCO(-) in the cold and dense regions of the interstellar medium where the anion could be formed through the association of abundant CO with still unobserved H(-).

Proposal for a laser control of vibrational cooling in Na(2) using resonance coalescence.

With a specific choice of laser parameters resulting in a so-called exceptional point (EP) in the wavelength-intensity parameter plane, it is possible to produce the coalescence of two Floquet resonances describing the photodissociation of the Na(2) molecule, which is one of the candidates for the formation of samples of translationally cold molecules. By appropriately tuning laser parameters along a contour encircling the exceptional point, the resonances exchange their quantum nature. Thus a laser-controlled transfer of the probability density from one field-free vibrational level to another is achieved through adiabatic transport involving these resonances. We propose an efficient scenario for vibrational cooling of Na(2) referring to cascade transfers involving multiple EPs and predicted to be robust up to a 78% rate against laser-induced dissociation.

Temperature dependence of binary and ternary recombination of D3+ ions with electrons.

Flowing and stationary afterglow experiments were performed to study the recombination of D(3)(+) ions with electrons at temperatures from 77 to 300 K. A linear dependence of apparent (effective) binary recombination rate coefficients on the pressure of the helium buffer gas was observed. Binary (D(3)(+)+e(-)) and ternary (D(3)(+)+e(-)+He) recombination rate coefficients were derived. The obtained binary rate coefficient agrees with recent theoretical values for dissociative recombination of D(3)(+). We describe the observed ternary process by a mechanism with two rate determining steps. In the first step, a rotationally excited long-lived neutral D(3)* is formed in D(3)(+)-e(-) collisions. As the second step, the D(3)* collides with a helium atom that prevents autoionization of D(3)*. We calculate lifetimes of D(3)* formed from ortho-, para-, or metastates of D(3)(+) and use the lifetimes to calculate ternary recombination rate coefficients.

Potential energy and dipole moment surfaces of H(3) (-) molecule.

A new potential energy surface for the electronic ground state of the simplest triatomic anion H(3) (-) is determined for a large number of geometries. Its accuracy is improved at short and large distances compared to previous studies. The permanent dipole moment surface of the state is also computed for the first time. Nine vibrational levels of H(3) (-) and 14 levels of D(3) (-) are obtained, bound by at most approximately 70 and approximately 126 cm(-1), respectively. These results should guide the spectroscopic search of the H(3) (-) ion in cold gases (below 100K) of molecular hydrogen in the presence of H(-) ions.

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.

Atom-molecule laser fed by stimulated three-body recombination.

Using three-body recombination as the underlying process, we propose a method of coherently driving an atomic Bose-Einstein condensate (BEC) into a molecular BEC. Superradiantlike stimulation favors atom-to-molecule transitions when two atomic BECs collide at a resonant kinetic energy, the result being two molecular BEC clouds moving with well-defined velocities. Potential applications include the construction of a molecule laser.

Mechanism for the destruction of H+3 ions by electron impact.

The rate at which the simplest triatomic ion (H+3) dissociates following recombination with a low-energy electron has been measured in numerous experiments. This process is particularly important for understanding observations of H+3 in diffuse interstellar clouds. But, despite extensive efforts, no theoretical treatment has yet proved capable of predicting the measured dissociative recombination rates at low energy, even to within an order of magnitude. Here we show that the Jahn-Teller symmetry-distortion effect-almost universally neglected in the theoretical description of electron-molecule collisions-generates recombination at a much faster rate than any other known mechanism. Our estimated rate constant overlaps the range of values spanned by experiments. We treat the low-energy collision process as a curve-crossing problem, which was previously thought inapplicable to low-energy recombination in H+3. Our calculation reproduces the measured propensity for three-body versus two-body breakup of the neutral fragments, as well as the vibrational distribution of the H2 product molecules.

Predissociation induced by ungerade-gerade symmetry breaking in 6Li7Li molecule

In the recent sub-Doppler experiment on the B1Pi(u) state of the Li2 molecule by Bouloufa et al. [J. Chem. Phys. 111, 1926 (1999)], where the dissociation of vibrational levels due to the tunneling through the potential barrier was investigated, several vibrational levels with abnormally large dissociated rates were observed in the case of the 6Li7Li isotopomer. This dynamical effect cannot be explained by tunneling as in the case of 6Li2 or 7Li2. A simple model of coupling between B1Pi(u) and 1(1)Pi(g) states involving the u-g symmetry breaking for 6Li7Li is proposed. Rates of the B1Pi(u) predissociated levels due to this coupling are calculated. A good agreement with the experiment is found.