Ab initio calculation of the ground and first excited states of the lithium dimer

Abstract

Abstract Based on a high level ab initio calculation which is carried out with the multireference configuration interaction method under the aug-cc-pVXZ (AVXZ) basis sets, X = T, Q, 5, the accurate potential energy curves (PECs) of the ground state X Σ g + 1 and the first excited state A Σ u + 1 of Li2 are constructed. By fitting the ab initio potential energy points with the Murrell–Sorbie potential function, the analytic potential energy functions (APEFs) are obtained. The molecular bond length at the equilibrium (R e ), the potential well depth (D e ), and the spectroscopic constants (B e , ω e , α e , and ω e χ e ) for the X Σ g + 1 state and the A Σ u + 1 state are deduced from the APEFs. The vibrational energy levels of the two electronic states are obtained by solving the time-independent Schrödinger equation with the Fourier grid Hamiltonian method. All the spectroscopic constants and the vibrational levels agree well with the experimental results. The Franck–Condon factors (FCFs) corresponding to the transitions from the vibrational level (v′ = 0) of the ground state to the vibrational levels (v″ = 0–74) of the first excited state have been calculated. The FCF for the vibronic transition of A Σ u + 1 (v″ = 0) ← X Σ g + 1 (v′ = 0) is the strongest. These PECs and corresponding spectroscopic constants provide reliable theoretical references to both the spectroscopic and the molecular dynamic studies of the Li2 dimer.