Studies of intramolecular and photoionization dynamics through the technique of time-resolved photoelectron imaging

A picosecond laser pulse (the pump) will be used to prepare a series of small molecules in electronically excited states and a time-delayed laser pulse (the probe) then used to ionize the excited molecules. Various combinations of the polarization of the pump and probe beams will be employed. The emitted photoelectrons will be detected through the technique of velocity map imaging. The time-resolved images will be analysed and interpreted using computational methods, enabling information on intramolecular and photoionization dynamics to be determined. In particular, these experiments can enable the extraction of quantitative information such as coupling coefficients, eigenstate energy separations and matrix elements, as well as insight into the identities of "doorway states" that promote efficient energy redistribution. They can also provide details of the partial wave composition of the photoelectron wavefunction. Comparisons between related molecular systems enable further mechanistic detail to be deduced.