Theoretical study of the CO2-O2 van der Waals complex: potential energy surface and applications.

A four-dimensional-potential energy surface (4D-PES) of the atmospherically relevant carbon dioxide-oxygen molecule (CO2-O2) van der Waals complex is mapped using the ab initio explicitly correlated coupled cluster method with single, double, and perturbative triple excitations (UCCSD(T)-F12b), and extrapolation to the complete basis set (CBS) limit using the cc-pVTZ-F12/cc-pVQZ-F12 bases and the l-3 formula. An analytic representation of the 4D-PES was fitted using the method of interpolating moving least squares (IMLS). These calculations predict that the most stable configuration of CO2-O2 complex corresponds to a planar slipped-parallel structure with a binding energy of V ∼ -243 cm-1. Another isomer is found on the PES, corresponding to a non-planar cross-shaped structure, with V ∼ -218 cm-1. The transition structure connecting the two minima is found at V ∼ -211 cm-1. We also performed comparisons with some CO2-X van der Waals complexes. Moreover, we provide a SAPT analysis of this molecular system. Then, we discuss the complexation induced shifts of CO2 and O2. Afterwards, this new 4D-PES is employed to compute the second virial coefficient including temperature dependence. A comparison between quantities obtained in our calculations and those from experiments found close agreement attesting to the high quality of the PES and to the importance of considering a full description of the anisotropic potential for the derivation of thermophysical properties of CO2-O2 mixtures.

Rydberg Electrons in a Bose-Einstein Condensate.

We investigate a hybrid system composed of ultracold Rydberg atoms immersed in an atomic Bose-Einstein condensate (BEC). The coupling between Rydberg electrons and BEC atoms leads to excitations of phonons, the exchange of which induces a Yukawa interaction between Rydberg atoms. Because of the small electron mass, the effective charge associated with this quasiparticle-mediated interaction can be large. Its range, equal to the BEC healing length, is tunable using Feshbach resonances to adjust the scattering length between BEC atoms. We find that for small healing lengths, the distortion of the BEC can "image" the Rydberg electron wave function, while for large healing lengths the induced attractive Yukawa potentials between Rydberg atoms are strong enough to bind them.

Quantum reactive scattering of O(3P)+H2 at collision energies up to 4.4 eV.

We report the results of quantum scattering calculations for the O((3)P)+H2 reaction for a range of collision energies from 0.4 to 4.4 eV, important for astrophysical and atmospheric processes. The total and state-to-state reactive cross sections are calculated using a fully quantum time-independent coupled-channel approach on recent potential energy surfaces of (3)A' and (3)A″ symmetry. A larger basis set than in the previous studies was used to ensure single-surface convergence at higher energies. Our results agree well with the published data at lower energies and indicate the breakdown of reduced dimensionality approach at collision energies higher than 1.5 eV. Differential cross sections and momentum transfer cross sections are also reported.

Giant formation rates of ultracold molecules via Feshbach-optimized photoassociation.

Ultracold molecules offer a broad variety of applications, ranging from metrology to quantum computing. However, forming "real" ultracold molecules, i.e., in deeply bound levels, is a very difficult proposition. Here, we show how photoassociation in the vicinity of a Feshbach resonance enhances molecular formation rates by several orders of magnitude. We illustrate this effect in heteronuclear systems, and find giant rate coefficients even in deeply bound levels. We also give a simple analytical expression for the photoassociation rate and discuss future applications of the Feshbach-optimized photoassociation technique.