Photophysical and photochemical molecular hole burning theory

Abstract

In this paper theories are given, describing photophysical and photochemical hole burning experiments on molecular mixed crystals at low temperature. Population saturation hole burning is treated for a two‐level system where the lower level is the ground state. Hole burning due to a triplet state acting as a population bottle neck is also described by a steady‐state density matrix theory. Connection is made with optical free induction decay. To obtain T₂ (the decay time of the off‐diagonal elements of the density matrix), which is the main goal of these hole burning experiments, a linear extrapolation method is discussed. For photochemical hole burning a time‐dependent density matrix treatment is given. Using this theory numerical simulations were performed of the experimental results obtained by Völker and co‐workers for porphin in n‐octane at low temperature. Good agreement with experiment is obtained. For this case extrapolation methods are discussed in order to obtain reliable T₂ values. A time‐dependent kinetic theory is used to simulate the photochemical hole burning experiments on dimethyl‐s‐tetrazine in durene and s‐tetrazine in benzene. This theory accounts for the recently revealed two‐photon character of these photodissociations. It is shown that despite this complication the hole full width at half‐maximum may still equal twice the homogeneous width of the S_o‐S₁ transition.