The adiabatic potential energy curves and the permanent and transition dipole moments of the low-lying electronic states of the NaLi molecule dissociating into Na(3s, 3p, 4s, 3d, 4p) + Li(2s, 2p, 3s, 3p, 3d) have been investigated. The molecular calculations are performed using an ab initio approach based on non-empirical pseudopotentials for Na+ and Li+ cores, parameterized l-dependent polarization potentials and full configuration interaction calculations through the CIPCI quantum chemistry package. The derived spectroscopic constants of the ground state and lower excited states are in good agreement with available experimental and theoretical works. However, the 7–101,3Σ+, 5–71Π, 2–63Π and 1–31,3Δ excited states are studied for the first time. The permanent dipole moment of NaLi has revealed both ionic characters relating to electron transfer and yielding Na+Li− and Na−Li+ arrangements. The transition dipole moment is used to evaluate the radiative lifetimes of the vibrational levels trapped in the 21Σ+ excited state for the first time. In addition to the bound–bound contribution, the bound-free term has been evaluated exactly using the Franck–Condon (FC) approximation and added to the total radiative lifetime.

For nearly all the states dissociating into Cs (6s, 6p, 5d, 7s, 7p, 6d, 8s) and Li (2s, 2p, 3s), we present an extensive adiabatic study for (1,3)Sigma(+), (1,3)Pi, and (1,3)Delta symmetries of the LiCs molecule. We have used an ab initio approach based on nonempirical pseudopotentials, parametrized l-dependent polarization potentials, and full configuration interaction calculations. A diabatisation procedure based on the effective Hamiltonian theory and an effective metric is used to produce the quasi-diabatic potential energy for all studied states. The spectroscopic constants (R(e), D(e), T(e), omega(e), omega(e)x(e), and B(e)) of these states are derived and compared with the available theoretical and experimental works. In addition to the potential energies, accurate permanent and transition dipole moment have been determined for a wide range of internuclear distances. The adiabatic permanent dipole moment for the first 10 (1)Sigma(+) electronic states has revealed ionic characters relating to electron transfer and yielding both Li(-)Cs(+) and Li(+)Cs(-) arrangements. The quasi-diabatic permanent moments show linear behaviors, especially at intermediate and large distance. The transition dipole moment between neighbor states has revealed many peaks located around the avoided crossing positions.