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The Journal of Chemical Physics

Photophysical and photochemical molecular hole burning theory

Harmen de Vries, Douwe A. Wiersma

Published Feb 1, 1980• 134 citations

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.

DOI: 10.1063/1.439330

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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.

Laser induced hole burning in optical absorption bands of low temperature solids has been investigated with emphasis on mechanisms for population hole burning, the interactions with the environment which limit the hole widths and the use of hole burning for ultra high resolution spectroscopy. Hole burning was observed in a wide range of solids including organic and organometallic molecules in crystals and rare earth ions in crystals and glasses. The mechanisms for hole burning also varied widely and a new mechanism involving optically induced nuclear spin flips of near neighbor nuclei was discovered. Examples of hole burning in new classes of materials are presented here for the first time, namely inorganic glasses (silicate glasses containing Nd(3+), Pr(3+) or Eu(3+)) and undoped stoichiometric compounds (e.g., EuP5O14). Hole recovery was used to determine nuclear spin lattice relaxation rates in praseodymium doped crystals. For allowed optical transitions (e.g., singlet states of zinc porphyrin, dibromoindigo and color centers in alkali halides) the hole widths at 2K are limited by population decay to approximately 50 MHz. For longer lived optical levels in crystalline materials, e.g., those containing rare earth ions, the hole widths are narrower (less than 10 MHz) and are limited by dynamical interactions with surrounding nuclei. In amorphous materials such as europium doped silicate glass, hole widths are much broader, being limited by low frequency tunneling motions. Hole burning measurements were complemented by time domain coherent transient (photon echo, and optical free decay) measurements of homogeneous linewidths which enabled us to measure optical resonances as narrow as 760 Hz in Eu(3+):Y2O3.

Photochemical hole burning (PHB) is a topic of attracting increasing interest from spectroscopic viewpoints as well as from the practical prospects for ultra-high-density frequency-domain optical storage. Recent advances in PHB study are reviewed mainly focusing on the effects of chemical structure of guest ions and molecules as well as host matrices on the efficiency of hole formation and its temperature dependence, low energy excitation modes and Debye-Waller factors in amorphous matrices, and the mechanism of photon-gated PHB.

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Excited state absorption measurements have usually to be modelled for the determination of the population densities in the different occupied excited states. Rate equations can be used for this purpose if the described experimental conditions are fulfilled. The photophysical hole burning (PPHB) effect may then be considered in an elementary way. Finally the decay rates of the different states and the holes can be determined. Fast routines for solving the system of differential equations are given allowing for an easy interactive analysis of the measurements on personal computers. The behaviour of the solutions for the two simplest models is discussed. The experimental results of PPHB measurements on crystal violet in 2-propanol were modelled using this formalism.

Photochemical Hole Burning (PHB) has attracted considerable interest not only as a tool for high resolution spectroscopy of amorphous solid at low temperature but also as a possible means for freguency-domain high-density optical storage.1) Many recent investigations have been devoted to a photon-gated mechanism because it allows nondestructive readout in utilizing PHB for a practical optical memory system. The mechanisms of previously reported photon-gated PHB systems are two-step photoionization, photodecomposition, and photoinduced donor-acceptor electron transfer reactions.1)