Processes and species encountered at high temperatures are important in a wide range of scientific and applied fields including combustion, atmospheric chemistry, and molecular astronomy. Understanding these reactions and molecules, however, is difficult due to the complex nature of the chemistry that occurs in extreme environments. I will present novel spectroscopic tools for attacking molecular questions in high temperature chemistry. A recent study of gauche-1,3-butadiene, a reactive intermediate in the prototypical Diels-Alder reaction, will be discussed, including issues of conjugation and strain.