New Horizons in Chemical and Photochemical Dynamics

Chemical change, whether caused by collisions between reactive atoms, radicals and molecules, or by absorption of light (photochemistry), is of fundamental importance in all branches of Chemistry. For example, synthesis of complicated organic molecules, such as those naturally occurring in plant and animal life, or needed to construct functional modern materials, requires an in-depth understanding of reaction mechanisms to design synthetic pathways. Ideas from physical chemistry based on thermodynamics and reaction rate theory underpin our ability to predict directions of chemical change and how quickly such change will occur. The fields of chemical reaction and photodissociation have sought to place such theories on a quantitative foundation built on deep understanding of the quantum mechanics of breakage and formation of chemical bonds. Potential energy surfaces (PESs) (based on the Born-Oppenheimer separation of the fast motion of light electrons from the slower motion of heavier atomic nuclei) are an essential concept because they provide a map of the energy landscape(s) over which chemical change occurs. Minima and barriers on the PESs correspond, respectively, to stable conformations of the atoms and short-lived transition states. Photodissociation involves dynamics on PESs lying higher in energy than the lowest, ground state, with the extra energy needed to reach these excited states provided by absorption of light. A powerful driver for advances in understanding of the dynamics of photochemical and reactive processes has been a close interaction between experimental and theoretical studies - arguably, the field has done much to stimulate the development of theoretical methods to calculate PE landscapes and describe the molecular dynamics on these surfaces. Such methods (subject to simplifying approximations) are now finding widespread use in molecular modelling of, for example, drug design, enzyme catalysis, and many other fields. The historical development of experimental and theoretical methods has relied on complementary studies of systems with only a small number of atoms (e.g. photodissociation of diatomic and triatomic molecules; reaction of atoms with diatomic molecules) so that accurate PESs can be computed and precise, quantum-mechanical (QM) scattering calculations carried out. Such experiments were mostly conducted in the gas phase, in the low-temperature and rarefied environment of a molecular beam, so that complicating factors of solvation, or interaction between molecules can be ignored. Considerable success with such systems has, for example, revealed the importance of exotic QM effects in chemistry such as tunnelling through reaction barriers, scattering resonances, non-adiabatic coupling between PESs, and interference between different pathways to the same products. For a photochemical or reactive system with 3 atoms, only 3 coordinates are required to describe all the possible arrangements of the atoms and the associated PEs can thus be computed for representative configurations spanning the entire PE landscape. We now seek a multi-pronged approach to extend such studies to more complicated systems, with the intention of learning about PE landscapes for larger molecules (for N atoms, 3N-6 coordinates are needed to describe the associated PE hypersurface), the effects of jumps between PE surfaces, and to examine how the energy landscapes and chemical dynamics are changed in the presence of solvent. In so doing, we will bring the fields of reaction and photodissociation dynamics closer to the types of chemical reactions used in synthesis by organic, inorganic and biological chemists. Our strategy involves development of new experiments and theoretical methods. The substantial challenges necessitate a consortium-based approach, in which complementary expertise in two Universities is brought together to address selected problems from which we can learn much about chemical change.