The Importance of Motions that Accompany Those Occurring Along the Reaction Coordinate

The reaction coordinate is a well known quantity used to define the motions critical to chemical reactions, but many other motions always accompany it. These other motions are typically ignored but this is not always possible. Sometimes it is not even clear as to which motions comprise the reaction coordinate: spectral measurements that one may assume are dominated by the reaction coordinate could instead be dominated by the accompanying modes. Examples of different scenarios are considered. The assignment of the visible absorption spectrum of chlorophyll-a was debated for 50 years, with profound consequences for the understanding of how light energy is transported and harvested in natural and artificial solar-energy devices. We recently introduced a new, comprehensive, assignment, the centrepiece of which was determination of the reaction coordinate for an unrecognized photochemical process. The notion that spectroscopy and reactivity are so closely connected comes directly from Hush's adiabatic theory of electron-transfer reactions. Its basic ideas are reviewed, similarities to traditional chemical theories drawn, key analytical results described, and the importance of the accompanying modes stressed. Also highlighted are recent advances that allow this theory to be applied to general transformations including isomerization processes, hybridization, aromaticity, hydrogen bonding, and understanding why the properties of first-row molecules such as NH3 (bond angle 108 degrees) are so different to those of PH3-BiH3 (bond angles 90-93 degrees). Historically, the question of what is the reaction coordinate and what is just an accompanying motion has not commonly been at the forefront of attention. In our new approach in which all chemical processes are described using the same core theory, this question becomes thrust forward as always being the most important qualitative feature to determine.