Photophysical and photochemical molecular hole burning theory
- 1 February 1980
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 72 (3) , 1851-1863
- https://doi.org/10.1063/1.439330
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 So‐S1 transition.Keywords
This publication has 60 references indexed in Scilit:
- Photochemical and Population Hole Burning in the Zero-Phonon Line of a Color Center—in NaFPhysical Review Letters, 1979
- Observation of transient intermediates in the photochemical decomposition of substituted s-tetrazinesJournal of the American Chemical Society, 1978
- Inhomogeneous broadening of local vibrations in spectra of organic molecules in solid matricesOptics Communications, 1977
- The nuclear quadrupole interaction in Pr3+:LaF3 — An optical-RF double resonance measurement of the ground electronic stateOptics Communications, 1977
- Observation of multiple optical hole burning in rubyOptics Communications, 1977
- The temperature broadening of purely electronic lines by the hole burning techniqueOptics Communications, 1977
- Direct observation of fluorescence narrower than the natural linewidthOptics Communications, 1976
- The homogeneous, pure electronic linewidth in the spectrum of a H2-phthalocyanine solution in n-octane at 5 KOptics Communications, 1976
- Stable ‘gap’ in absorption spectra of solid solutions of organic molecules by laser irradiationOptics Communications, 1974
- Observation du “hole burning” dans une solution de cryptocyanine dans le methanolOptics Communications, 1973