We show theoretically with the simplest possible model that the intensity of an upconversion luminescence that is excited by the sequential absorption of n photons has a dependence on absorbed pump power P, which may range from the limit of P n down to the limit of P 1 for the upper state and less than P 1 for the intermediate states. The two limits are identified as the cases of infinitely small and infinitely large upconversion rates, respectively. In the latter case, the dependence of luminescence intensities from intermediate excited states on pump power changes with the underlying upconversion and decay mechanisms. In certain situations, energytransfer upconversion and excited-state absorption can be distinguished by the measured slopes. The competition between linear decay and upconversion in the individual excitation steps of sequential upconversion can be analyzed. The influence of nonuniform distributions of absorbed pump power or of a subset of ions participating in energy-transfer upconversion is investigated. These results are of importance for the interpretation of excitation mechanisms of luminescent and laser materials. We verify our theoretical results by experimental examples of multiphoton-excited luminescence in Cs 3 Lu 2 Cl 9 :Er 3ϩ , Ba 2 YCl 7 :Er 3ϩ , LiYF 4 :Nd 3ϩ , and Cs 2 ZrCl 6 :Re 4ϩ .

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Recent spectroscopic results in the emerging area of transition-metal NIR-to-visible upconversion are related. The examples of Ti(2+)-, Re(4+)-, and Os(4+)-doped materials showing upconversion illustrate GSA/ESA, GSA/ETU, and photon avalanche multiphoton excitation mechanisms, respectively. Strategies for manipulation of such upconversion processes using the spectroscopic or magnetic properties of the host material are described. High-resolution low-temperature continuous-wave absorption and emission and time-resolved emission experiments combine to yield information about energy splittings, intensities, and excited-state dynamics, and assist in the design and development of luminescent materials showing novel multiphoton excitation properties.

The magnetic properties of oxo-bridged oxo-(carboxylato)-bridged and oxo-bis(carboxylato)-bridged iron(III) dimers are found to depend on the iron−(μ-O) distance as well as on the iron−(μ-O)−iron angle. With an angular and radial overlap model we account for both these dependencies. The use of an angular overlap model allows us to separate the σ donor properties of oxide as a ligand into the sσ and pσ contributions.