This thesis consists of two parts. The first part is focused on the high resolution infrared-infrared (IRIR) double resonance spectroscopy study of the Rubidium dimer triplet ground state a3Sigma u+. We have observed fluorescence to this state for J=30, 50 and 70 rotational quantum numbers. We have used a perturbed pair of rovibrational levels in the a3Sigmau + ∼ b3piu electronic states as an intermediate excitation step to the higher lying 2 3pig state to get access by fluorescence decay to thea3Sigmau+ state. This allowed us to calculate the term values and the potential energy curve for the triplet ground state.;The second part of the thesis is a computational study of lifetimes and transition dipole moment matrix elements for the sodium dimer ion pair states of 1Sigmag+ symmetry. These calculated parameters will be helpful for the design of a quadruple resonance based Autler-Townes spectroscopic probe of the transition dipole moments between these states and the A1Sigma u+ state. The calculated lifetime values compare well with results from literature when available.;This work was supported by the National Science Foundation through awards PHY 0245311, PHY 0555608 and PHY 0855502. |