Determination of microscopic parameters for nonresonant energy-transfer processes in rare-earth-doped crystals

A method for estimating the microscopic probability rate of phonon-assisted energy transfer between rare-earth $\mathrm{}(3+)\mathrm{}$ ions in solids was developed based on Dexter’s theory for phonon-assisted energy transfer. The proposed method in this paper enables one to calculate the overlap integral from fundamental cross-section spectra of nonresonant energy transfer involving a multiphonon generation in both donor and acceptor sites. A translation of the donor emission spectrum towards the acceptor absorption scaled with the $N$-phonon emission probability represents the $m$-phonon emission band which performs the energy transfer to the acceptor. A nonvanishing overlap integral ${10}^{-2}–{10}^{-3}$ times smaller than for the resonant case is found. A multiphonon generation probability assisting the energy transfer was considered due to a combined mechanism of creation and annihilation of phonons. The participation of each phonon in the process was determined. This method was used to investigate the ${\mathrm{Tm}}^{3+}{(}^3{F}_4)\to {\mathrm{Ho}}^{3+}{(}^5{I}_7),{\mathrm{Er}}^{3+}{(}^4{I}_{13/2})\to [{\mathrm{Ho}}^{3+}{(}^5{I}_7),{\mathrm{Tm}}^{3+}{(}^3{F}_4)]$ direct energy transfers in ${\mathrm{LiYF}}_4$ crystals, as well the back transfers.