ATR-FTIR and density functional theory study of the structures, energetics, and vibrational spectra of phosphate adsorbed onto goethite.

Periodic plane-wave density functional theory (DFT) and molecular cluster hybrid molecular orbital-DFT (MO-DFT) calculations were performed on models of phosphate surface complexes on the (100), (010), (001), (101), and (210) surfaces of α-FeOOH (goethite). Binding energies of monodentate and bidentate HPO(4)(2-) surface complexes were compared to H(2)PO(4)(-) outer-sphere complexes. Both the average potential energies from DFT molecular dynamics (DFT-MD) simulations and energy minimizations were used to estimate adsorption energies for each configuration. Molecular clusters were extracted from the energy-minimized structures of the periodic systems and subjected to energy reminimization and frequency analysis with MO-DFT. The modeled P-O and P---Fe distances were consistent with EXAFS data for the arsenate oxyanion that is an analog of phosphate, and the interatomic distances predicted by the clusters were similar to those of the periodic models. Calculated vibrational frequencies from these clusters were then correlated with observed infrared bands. Configurations that resulted in favorable adsorption energies were also found to produce theoretical vibrational frequencies that correlated well with experiment. The relative stability of monodentate versus bidentate configurations was a function of the goethite surface under consideration. Overall, our results show that phosphate adsorption onto goethite occurs as a variety of surface complexes depending on the habit of the mineral (i.e., surfaces present) and solution pH. Previous IR spectroscopic studies may have been difficult to interpret because the observed spectra averaged the structural properties of three or more configurations on any given sample with multiple surfaces.

Resonant X-ray enhancement of the Auger effect in high-Z atoms, molecules, and nanoparticles: potential biomedical applications.

It is shown that X-ray absorption can be considerably enhanced at resonant energies corresponding to K-shell excitation into higher shells with electron vacancies following Auger emissions in high-Z elements and compounds employed in biomedical applications. We calculate Auger resonant probabilities and cross sections to obtain total mass attenuation coefficients with resonant cross sections and detailed resonance structures corresponding to Kalpha, Kbeta, Kgamma, Kdelta, and Keta complexes lying between 6.4-7.1 keV in iron and 67-80 keV in gold. The basic parameters were computed using the relativistic atomic structure codes and the R-matrix codes. It is found that the average enhancement at resonant energies is up to a factor of 1000 or more for associated K --> L, M, N, O, P transitions. The resonant energies in high-Z elements such as gold are sufficiently high to ensure significant penetration in body tissue, and hence the possibility of achieving X-radiation dose reduction commensurate with resonant enhancements for cancer theranostics using high-Z nanoparticles and molecular radiosensitizing agents embedded in malignant tumors. The in situ deposition of X-ray energy, followed by secondary photon and electron emission, will be localized at the tumor site. We also note the relevance of this work to the development of novel monochromatic or narrow-band X-ray emission sources for medical diagnostics and therapeutics.