Measurement and model calculation of the temperature dependence of ligand-to-metal energy transfer rates in lanthanide complexes

Temperature dependent transient curves of excited levels of a model Eu3+ complex have been measured for the first time. A coincidence between the temperature dependent rise time of the 5D0 emitting level and decay time of the 5D1 excited level in the [Eu(tta)3(H2O)2] complex has been found, which unambiguously proves the T1→5D1→5D0 sensitization pathway. A theoretical approach for the temperature dependent energy transfer rates has been successfully applied to the rationalization of the experimental data.

Tb3+-> Eu3+ Energy Transfer in Mixed-Lanthanide-Organic Frameworks

In this work, we report a theoretical and experimental investigation of the energy transfer mechanism in two isotypical 2D coordination polymers, (infinity)[(Tb1-xEux)(DPA)(HDPA)], where H(2)DPA is pyridine 2,6-dicarboxylic acid and x = 0.05 or 0.50. Emission spectra of (infinity)[(Tb0.95Eu0.05)(DPA)(HDPA)] and (infinity)[(Tb0.5Eu0.5)(DPA)(HDPA)], (I) and (2), show that the high quenching effect on Tb3+ emission caused by Eu3+ ion indicates an efficient Tb3+-> Eu3+ energy transfer (ET). The k(ET) of Tb3+-> Eu3+ ET and rise rates (k(r)) of Eu3+ as a function of temperature for (1) are on the same order of magnitude, indicating that the sensitization of the Eu3+5D0 level is highly fed by ET from the D-5(4) level of Tb3+ ion. The eta(ET) and R-0 values vary in the 67-79% and 7.15 to 7.93 angstrom ranges. Hence, Tb3+ is enabled to transfer efficiently to Eu3+ that can occupy the possible sites at 6.32 and 6.75 angstrom. For (2), the ET processes occur on average with eta(ET) and R-0 of 97% and 31 angstrom, respectively. Consequently, Tb3+ ion is enabled to transfer energy to Eu3+ localized at different layers. The theoretical model developed by Malta was implemented aiming to insert more insights about the dominant mechanisms involved in the ET between lanthanides ions. Calculated single Tb3+-> Eu3+ ETs are three orders of magnitude inferior to those experimentally; however, it can be explained by the theoretical model that does not consider the role of phonon assistance in the Ln(3+)-> Ln(3+) ET processes. In addition, the Tb3+-> Eu3+ ET processes are predominantly governed by dipole-dipole (d-d) and dipole-quadrupole (d-q) mechanisms.

Near-infrared quantum cutting through a three-step energy transfer process in Nd3+-Yb3+ co-doped fluoroindogallate glasses

The Nd3+-Yb3+ couple was investigated in fluoroindogallate glasses using optical spectroscopy to elucidate the energy transfer mechanisms involved in the downconversion (DC) process. Upon excitation of a Nd3+ ion by an ultraviolet photon, DC through a three-step energy transfer process occurs, in which the energy of the ultraviolet photon absorbed by the Nd3+ ion is converted into three infrared photons emitted by Yb3+ ions, i.e. quantum cutting (QC). In addition, with excitation in the visible, our results confirm that the DC process occurs through a one-step energy transfer process, in which the energy of a visible photon absorbed by the Nd3+ ion is converted into only one infrared photon emitted by an Yb3+ ion. Time-resolved measurements enabled the estimation of the efficiencies of the cross-relaxation processes between Nd3+ and Yb3+ ions.

A MODIS-Based Energy Balance to Estimate Evapotranspiration for Clear-Sky Days in Brazilian Tropical Savannas

Evapotranspiration (ET) plays an important role in global climate dynamics and in primary production of terrestrial ecosystems; it represents the mass and energy transfer from the land to atmosphere. Limitations to measuring ET at large scales using ground-based methods have motivated the development of satellite remote sensing techniques. The purpose of this work is to evaluate the accuracy of the SEBAL algorithm for estimating surface turbulent heat fluxes at regional scale, using 28 images from MODIS. SEBAL estimates are compared with eddy-covariance (EC) measurements and results from the hydrological model MGB-IPH. SEBAL instantaneous estimates of latent heat flux (LE) yielded r(2) = 0.64 and r(2) = 0.62 over sugarcane croplands and savannas when compared against in situ EC estimates. At the same sites, daily aggregated estimates of LE were r(2) = 0.76 and r(2) = 0.66, respectively. Energy balance closure showed that turbulent fluxes over sugarcane croplands were underestimated by 7% and 9% over savannas. Average daily ET from SEBAL is in close agreement with estimates from the hydrological model for an overlay of 38,100 km(2) (r(2) = 0.88). Inputs to which the algorithm is most sensitive are vegetation index (NDVI), gradient of temperature (dT) to compute sensible heat flux (H) and net radiation (Re). It was verified that SEBAL has a tendency to overestimate results both at local and regional scales probably because of low sensitivity to soil moisture and water stress. Nevertheless the results confirm the potential of the SEBAL algorithm, when used with MODIS images for estimating instantaneous LE and daily ET from large areas.