The Ab Initio Design of Efficient Photoinitiators

We have employed ab initio quantum chemical methods to model a set of both existing and new photoinitiators (PI) and synthesized and characterized several PIs that are predicted to be promising. Calculations of existing PIs are used to benchmark the specific computational methods as well as to develop a fundamental understanding of the various phenomena involved in the photoinitiation process. We then use quantum chemistry to computationally prototype a series of new PIs by calculating a set of properties for each case, including; absorption peak, oscillator strength/absorbtivity, bond dissociation energy, radical reactivity and properties related to the rate of intersystem crossing. We have synthesized and characterized several new PIs, including derivatives of the phosphine oxide and the benzoyl germanium PIs. These experiments confirm the ab initio predictions and provide additional feedback to the computational prototyping effort.