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Physical review. B, Solid state

Phonon-assisted radiative transfer

Theodore D. Holstein, S. K. Lyo, R. Orbach

Published Jul 15, 1977• 37 citations
Publisher

Abstract

The radiative-transfer rate for inhomogeneously broadened optical lines is calculated. Photon emission and absorption is supplemented by one- and two-phonon processes to achieve energy conservation. These photon-assisted radiative transfer processes are shown to be effective at low concentrations, where electrostatic and exchange processes are weak, in the intermediate or strong radiative trapping regime. Specific application is made to the case of dilute ruby, and explicit transfer rates are calculated. The coherence factors, which undermine nonradiative single-phonon-assisted energy transfer for a small energy mismatch, are not important for radiative transfer, if the photon mean free path is longer than the wavelength of the energy matching phonon. The one-phonon process is found to vary linearly with temperature, and to be independent of the energy mismatch. However, the calculated rate for the case of ruby is found to be very slow. The two-phonon-assisted radiative-transfer process rates are calculated. They dominate the one-phonon-assisted rate for all reasonable temperatures. The results of an earlier paper are shown to be related to phonon-assisted radiative transfer if one replaces the exchange coupling between transfer sites $J$ by $\ensuremath{\sim}\frac{{\ensuremath{\tau}}_{R}^{\ensuremath{-}1}\ensuremath{\hbar}}{(\frac{{r}_{0}}{\ensuremath{\lambda}})}$. Here ${\ensuremath{\tau}}_{R}$ is the radiative lifetime, ${r}_{0}$ the distance between sites, and $\ensuremath{\lambda}$ the photon wavelength involved in the radiative transfer. This replacement results in a line center to wing transfer rate equal to 1.1 \ifmmode\times\else\texttimes\fi{} ${10}^{2}$ ${e}^{\ensuremath{-}\frac{42}{T}}$ ${\mathrm{sec}}^{\ensuremath{-}1}$ for ruby (independent of concentration for a photon mean free path smaller than the sample size).

DOI
10.1103/physrevb.16.934

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Optics Letters•Sep 1, 1977•25 citations
The radiative-transfer rate for inhomogeneously broadened optical lines is calculated. Photon emission and absorption is supplemented by one- and two-phonon processes to achieve energy conservation. These photon-assisted radiative transfer processes are shown to be effective at low concentrations, where electrostatic and exchange processes are weak, in the intermediate or strong radiative trapping regime. Specific application is made to the case of dilute ruby, and explicit transfer rates are calculated. The coherence factors, which undermine nonradiative single-phonon-assisted energy transfer for a small energy mismatch, are not important for radiative transfer, if the photon mean free path is longer than the wavelength of the energy matching phonon. The one-phonon process is found to vary linearly with temperature, and to be independent of the energy mismatch. However, the calculated rate for the case of ruby is found to be very slow. The two-phonon-assisted radiative-transfer process rates are calculated. They dominate the one-phonon-assisted rate for all reasonable temperatures. The results of an earlier paper are shown to be related to phonon-assisted radiative transfer if one replaces the exchange coupling between transfer sites JJJ by \ensuremath∼\ensuremathτR\ensuremath−1\ensuremathℏ(r0\ensuremathλ)\ensuremath{\sim}\frac{{\ensuremath{\tau}}_{R}^{\ensuremath{-}1}\ensuremath{\hbar}}{(\frac{{r}_{0}}{\ensuremath{\lambda}})}\ensuremath∼(\ensuremathλr0​​)\ensuremathτR\ensuremath−1​\ensuremathℏ​. Here \ensuremathτR{\ensuremath{\tau}}_{R}\ensuremathτR​ is the radiative lifetime, r0{r}_{0}r0​ the distance between sites, and \ensuremathλ\ensuremath{\lambda}\ensuremathλ the photon wavelength involved in the radiative transfer. This replacement results in a line center to wing transfer rate equal to 1.1 \ifmmode\times\else\texttimes\fi{} 102{10}^{2}102 e\ensuremath−42T{e}^{\ensuremath{-}\frac{42}{T}}e\ensuremath−T42​ sec\ensuremath−1{\mathrm{sec}}^{\ensuremath{-}1}sec\ensuremath−1 for ruby (independent of concentration for a photon mean free path smaller than the sample size).
Systematic investigations of the effect of self-absorption on the dynamic and steady-state spectroscopic properties in ruby have been carried out at different temperatures (from approximately 130 to 500 K) using a long, pink laser rod. At about 140 K,the lengthening of decay times of the R lines reached a maximum and then decreased with increasing geometric trapping. Spectral diffusion as large as 10 cm -1 was observed in the complete-trapping regime. These observations suggest reexamination of the theoretical model for phonon-assisted radiative energy transfer in ruby.
We have measured the radiative efficiency (ratio of RRR-line photons to the total number of photons emitted) and absorption cross sections for the RRR lines of dilute ruby, as a function of polarization and temperature between 20 and 373\ifmmode^\circ\else\textdegree\fi{}K. We have also measured the fluorescent lifetime from 20 to 373\ifmmode^\circ\else\textdegree\fi{}K in optically thin crystals, and from 20 to 273\ifmmode^\circ\else\textdegree\fi{}K in optically thick crystals. The difference between the reciprocal lifetimes in thin and thick crystals is directly comparable (via the Einstein relations) with the integrated absorption in the RRR lines. This comparison shows that for the RRR lines at 20 and 77\ifmmode^\circ\else\textdegree\fi{}K detailed balance holds to well within the experimental error of 5%, a precision never to our knowledge previously approached in solids. An upper limit of 0.002 ${\mathrm{cm}}^{\ensuremath{-}1}$ was placed on any Stokes shift of the R1{R}_{1}R1​ line, confirming that it is a no-phonon line. Comparison of $\ensuremath{\sigma}$ and $\ensuremath{\alpha}$ spectra confirms that the RRR lines and their vibronic satellites are predominately electric-dipole in character. The radiative efficiency of the RRR lines is strongly polarization dependent, a result which differs from that of previous workers. Its temperature dependence agrees well with that calculated from the observed vibronic spectrum at 77\ifmmode^\circ\else\textdegree\fi{}K. The integrated absorption in the RRR lines increases by about 20% between 20 and 373\ifmmode^\circ\else\textdegree\fi{}K. The absorption in the vibronic satellites on the high-frequency side of the RRR lines appears to be weaker than the corresponding emission on the low-frequency side. The temperature variation of the lifetime agrees well with that calculated from the absorption and radiative efficiency, but about 10% of the decay at 77\ifmmode^\circ\else\textdegree\fi{}K and 30% at 373\ifmmode^\circ\else\textdegree\fi{}K is either nonradiative or by emission at wavelengths outside the range of observation. The implications of our results for laser work are discussed.
The first experimental evidence for distinct spectral and spatial energy transfer in ruby via nonradiative coupling is presented. Monochromatic laser excitation of the R1{R}_{1}R1​ line results in a rise of the inhomogeneous background on a millisecond time scale, consistent with a one-phonon---assisted process and contrary to recent theory. However, time-resolved studies of trap fluorescence suggest a rapid, coherent, spatial transfer within the R1{R}_{1}R1​ line which does not shift frequency.
Recent experiments have demonstrated Anderson localization in inhomogeneously broadened paramagnetic spin systems. We examine two-phonon processes which can frequency shift the individual spin packets, and thereby allow energy transfer to take place. We make specific application to ruby, and show that the dominant phonon-induced energy-transfer rate is directly proportional to the (spin-nonflip) $\overline{E}\ensuremath{\rightarrow}2\overline{A}$ rate [varying as $\mathrm{exp}(\ensuremath{-}\frac{42}{T})$], and inversely proportional to the square of the energy mismatch of the participating spin packets.