The formation of propellant dark zone (DZ) structures in the gaseous flames above many solid propellants has been a subject of recurrent interest to us for about 20 years. The DZ structure is controlled by small molecule chemistry. The DZ chemistry is very important in controlling both the flame structure at low pressure (10-100 atm) and burning rates at high pressure (above similar to 500 atm), even though DZs collapse at higher pressures. We developed a detailed, frequently updated mechanism to model it. This report reviews prior work, introduces our most recent modeling results, and documents the first quantitative tests of several key assumptions. All relevant experimental literature is critically assessed to identify datasets for testing our model. Comparison of predictions and experimental results shows reasonable agreement, and thus we advocate use of our mechanism. But the precision of both experiments and predictions is not tight, nor are there many test datasets. Further experimentation is needed, and types of study that would be of greatest benefit are suggested. A detailed discussion of the chemistry that controls DZ structure is presented. Published by Elsevier Inc. on behalf of The Combustion Institute.