There is considerable interest in the need to improve the operation of systems which can potentially serve as alternate energy sources. Entailed in this effort is the desire to understand the vapor phase chemistry and compounds which may enter as by-products of the system under consideration. These compounds may have deleterious effects on the gas phase chemistry or play an important role through high temperature gas-solid corrosion kinetics. Here we outline the nature of the problem and focus on a subset of these molecules, the metal hydroxides and the alkali oxides and sulfides. A critical analysis of the data base is presented and new experiments are outlined which encompass the investigation of thermochemistry and the evaluation of molecular parameters through the study of visible, infrared, microwave and electron spin resonance (ESR) spectroscopy. Recent chemiluminescent experiments which lead to the evaluation of a new stringent lower bound for the K-OH band energy are summarized. This stringent lower bound (88.2 kcal/mole) correlates within the quoted error bounds with the absolute upper bound of previous experimental determinations. Preliminary laser fluorescence studies on Na20 are reported and the possible influence of "ultrafast" energy transfer (E-E and V-E transfer among the excited states of high temperature molecules) on the behavior of energy generating systems is noted.