We present a theoretical study on the potential energy surface and bound states of He–A 2 + complexes, where A is one of the alkali Li or Na atoms. The intermolecular interactions were systematically investigated by high-level ab initio electronic structure computations, and the corresponding raw data were then employed to reproduce accurate analytical expressions of the potential surfaces. In turn, we used these potentials to evaluate bound configurations of the trimers from nuclear quantum calculations and to extract information on the effect of orientational anisotropy of the forces and the interplay between repulsive and attractive interaction within the potential surfaces. The spatial features of the bound states are analyzed and discussed in detail. We found that both systems are going under large amplitude stretching and bending motions with high zero-point energies. Despite the large differences in the potential well-depths, the correct treatment of nuclear quantum effects provides insights on the effect of different strength of the ionic interaction on the spectral structure of such cationic alkali van der Waals complexes, related to the mobility of ions and the formation of cold-molecules in He-controlled environments.
Synopsis Doped He droplets constitute an important environment as ultracold homogeneous matrices for spectroscopic studies. Alkali metal dopants have a series of interesting properties due to their unusual bonding behavior. Neutral atoms attached to the surface of the droplet, forming eventually cold molecules via collisions, while charged dopants form solvation shells, related with the low mobility of the ions in experiments. So, investigations on the underlying intermolecular, markedly orientational ionic, forces, and on the miscoscopic structures of alkali-cation-He complexes is essential.
Helium dimer in its metastable triplet electronic state, He
2(a 3Σu+), is a promising candidate for direct laser cooling and precision measurements. Interactions and collisions involving He
2(a 3Σu+) remain unexplored in ultracold and cold energy domains. Here, we present the first theoretical investigation of intermolecular interactions and collision dynamics of He
2(a 3Σu+)+Ne van der Waals complex. For the ground electronic state,
X 3A′, we employ a spin-restricted coupled cluster method with single, double, and noniterative triple excitations. The resulting interaction potential exhibits an extremely shallow well with a depth of 4.612 cm
−1. We construct a three-dimensional vibrationally averaged potential energy surface. Using this surface, we perform full close-coupling calculations including fine-structure levels of He
2(a 3Σu+) to investigate collisional excitation and quenching induced by Ne. We analyze the low-energy scattering dynamics and model resonant features associated with quasi-bound states supported by interaction potential. Propensity rule for fine-structure conserving transitions is established. We additionally consider He
2+Ar collisions and compare their energy dependence and resonance structure with those of He
2+Ne. The He
2+Ar system exhibits a richer resonance structure, highlighting the sensitivity of low-energy scattering to interaction potential and reduced mass. Calculated PES and scattering properties provide a reliable benchmark for description of He
2+Ne van der Waals complex and may be useful for interpretation of future experimental spectra and collision measurements.
Abstract The present article is related to a talk presented during the Symposium on Coherent Control and Ultracold Chemistry held during the Sixth Congress of the International Society for Theoretical Chemical Physics (ISTCP‐VI, July 2008). The talk was entitled “Electronic structure properties of alkali dimers and trimers. Prospects for alignment of ultracold molecules.” Here we report on the electrostatic repulsion forces of the ionic cores at short separation, involved when the potential energy surfaces of alkali trimers are calculated with a quantum chemistry approach based on effective large‐core potentials for ionic core description. We demonstrate that such forces in the triatomic molecule can be obtained as the sum of three pairwise terms. We illustrate our results on the lowest electronic states of Cs3, which are computed for the first time within a full configuration interaction based on a large Gaussian basis set. As a preliminary section, we also propose a brief introduction about the importance of alkali trimer systems in the context of cold and ultracold molecules. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009
The present paper is related to a talk presented during the Symposium on Coherent Control and Ultracold Chemistry held during the Sixth Congress of the International Society for Theoretical Chemical Physics (ISTCP-VI, July 2008). The talk was entitled "Electronic structure properties of alkali dimers and trimers. Prospects for alignment of ultracold molecules". Here we report on the electrostatic repulsion forces of the ionic cores at short separation, involved when the potential energy surfaces of alkali trimers are calculated with a quantum chemistry approach based on effective large-core potentials for ionic core description. We demonstrate that such forces in the triatomic molecule can be obtained as the sum of three pairwise terms. We illustrate our results on the lowest electronic states of Cs
3, which are computed for the first time within a full configuration interaction based on a large Gaussian basis set. As a preliminary section, we also propose a brief introduction about the importance of alkali trimer systems in the context of cold and ultracold molecules.
) with alkali-metal (Li, Na, K, Rb, Cs) and alkaline-earth-metal (Mg, Ca, Sr, Ba) atoms. State-of-the-art ab initio techniques are applied to compute the potential energy surfaces (PESs) for these systems. The coupled cluster method restricted to single, double, and noniterative triple excitations, CCSD(T), is employed and the scalar relativistic effects in heavier metal atoms are modeled within the small-core energy-consistent pseudopotentials. The leading long-range isotropic and anisotropic induction and dispersion interaction coefficients are obtained within the perturbation theory. The PESs are characterized in detail and their universal similarities typical for systems dominated by the induction interaction are discussed. The two-dimensional PESs are provided for selected systems and can be employed in scattering calculations. The possible channels of chemical reactions and their control are analyzed based on the energetics of the reactants. The present study of the electronic structure is the first step towards the evaluation of prospects for sympathetic cooling and controlled chemistry of linear polyatomic ions with ultracold atoms.
We theoretically characterize interactions, energetics, and chemical reaction paths in ionic two-body and three-body systems of alkali-metal and alkaline-earth-metal atoms in the context of modern experiments with cold hybrid ion-atom mixtures. Using ab initio techniques of quantum chemistry such as the coupled-cluster method, we calculate ground-state electronic properties of all diatomic
AB+ and most of the triatomic
A2B+ molecular ions consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and Yb atoms. Different geometries and wave-function symmetries of the ground state are found for different classes of molecular ions. We analyze intermolecular interactions in the investigated systems including additive two-body and nonadditive three-body ones. As an example we provide two-dimensional interaction potential-energy surfaces for
KRb++K and
Rb++Sr2 mixtures. We identify possible channels of chemical reactions based on the energetics of the reactants. The present results may be useful for investigating controlled chemical reactions and other applications of molecular ions formed in cold hybrid ion-atom systems.