State transitions which permit the identification of the molecular species in dense interstellar clouds are reviewed, along with the techniques used to calculate the transition energies, the database on known molecular transitions and the accuracy of the values. The transition energies cannot be measured directly and therefore must be modeled analytically. Scattering theory is used to determine the intermolecular forces on the basis of quantum mechanics. The nuclear motions can also be modeled with classical mechanics. Sample rate constants are provided for molecular systems known to inhabit dense interstellar clouds. The values serve as a database for interpreting microwave and RF astrophysical data on the transitions undergone by interstellar molecules.