Ab Initio Calculations of the Electronic Structure of the Doublet and Quartet States of the Rubidium Trimer

• Published in: Optics and spectroscopy Vol. 132; no. 3; pp. 223 - 233
• Main Authors: Bormotova, E. A., Likharev, A. S., Stolyarov, A. V.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 2024; Springer Nature B.V
• Subjects: Angular momentum; Chemical synthesis; Configuration interaction; Configuration management; Couplings; Dipole moments; Electron spin; Electronic structure; Electrons; Laser cooling; Lasers; Mathematical analysis; Molecular orbitals; Molecular structure; Optical Devices; Optics; Photonics; Physics; Physics and Astronomy; Potential energy; Quantum chemistry; Rubidium; Self consistent fields; Triangles; Trimers; ultracold molecules; transition probabilities; Rubidium; excited states; spin-orbit coupling; molecular electronic structure
• ISSN: 0030-400X; 1562-6911
• DOI: 10.1134/S0030400X24030044

Systematic quantum chemical calculations were performed for the ground and a number of low-lying electronically excited doublet and quartet states of the rubidium trimer molecule. The obtained potential energy surfaces (PES), spin-orbit couplings (SOC) and electronic transition dipole moments (ETDM) can be useful for optimizing paths for laser synthesis, cooling and manipulation of stable ensembles of Rb 3  molecules at ultralow temperatures. Ab initio calculations of the electronic structure of the homonuclear Rb 3 molecule, in linear, isosceles triangle and equilateral triangle geometries, were performed using the multi-reference configuration interaction method, taking into account single and double excitations (M-R‑CISD) and with explicit dynamic correlation of only the three valence electrons. The structure of each atom was approximated using a nine-electron effective core potential (ECP28MDF), and molecular orbitals (MOs) were optimized using the spin averaged (over doublet and quartet states) multi-configuration self-consistent field (SA-CASSCF) method. Core–valence correlations between twenty-four subvalence electrons located on doubly occupied MOs and three valence electrons were implicitly taken into account using a one-electron angular momentum-independent Müller–Mayer core polarization potential (CPP). As a result of topological investigations at over 35 000 points, two dimensional PES, SOC, and ETDM functions were obtained and the geometric parameters Rb 3 were found at which the most intense vertical transitions and the maximum influence of the SOC are expected.