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Mixed anatase/rutile TiO2 exhibits high photocatalytic activity; however, the mechanism underlying the high performance of the mixed phases is not fully understood. We have performed time-domain ab initio calculations to study the exited state dynamics in mixed phase TiO2 and to investigate the impact of an oxygen vacancy on the dynamics. The anatase(100)/rutile(001) heterostructures with and without an oxygen vacancy used in this work exhibit type II band alignment with the conduction band of rutile residing above that of anatase. The oxygen vacancy introduces a hole trap state inside the bandgap. Owing to a strong coupling between the donor and acceptor states, the electron and hole transfers across the anatase/rutile interface occur on an ultrafast 100 fs timescale in both systems. The decoupling of electron and hole favors a long-lived charge separated state. The electron–hole recombination across the pristine anatase/rutile interface takes 6.6 ns and is significantly slower than that in the pure anatase and rutile phases, showing good agreement with experiments. The electron transfer dynamics is independent of the oxygen vacancy, which has some influence on the hole transfer and a strong effect on carrier recombination. By creating a hole trap state, the vacancy accelerates carrier losses by over an order of magnitude. The fast charge separation and the long lifetime of the charge separated state rationalize the enhanced photocatalytic performance of mixed phase TiO2 compared to the pure phases. [ABSTRACT FROM AUTHOR]

We present a measurement of molecular orientation of water at charged surfactant aqueous interfaces as a function of surface charge density. The polarization dependent spectral line shapes of the water bend mode were measured by vibrational sum-frequency generation at the positively charged surfactant cetyltrimethylammonium bromide (CTAB)/water interface and negatively charged surfactant sodium dodecyl sulfate/water interface. Orientational analysis using the water bend mode as a vibrational probe, within the electric dipole approximation, reveals structural differences between these surfaces and quantifies how different hydrogen bonded species re-orient around the surfactant head groups as the surface charge density changes. As the concentration of the positively charged surfactant (CTAB) increases, the surface water molecules with free-OH groups reorient their hydrogen away from the bulk water and the C2v axis closer to the surface normal. This suggests that these free-OH molecules are in general located above the positively charged head groups of CTAB, and thus, the charge-dipole interaction pulls their oxygen "down" and pushes hydrogen "up." On the contrary, water molecules with two donor hydrogen bonds re-orient their hydrogen toward the bulk water, likely because most of these molecules are below the CTAB surfactant head groups. [ABSTRACT FROM AUTHOR]

Molecular organization of vapor-deposited organic molecules in the active layer of organic light-emitting diodes (OLEDs) has been a matter of great interest as it directly influences various optoelectronic properties and the overall performance of the devices. Contrary to the general assumption of isotropic molecular orientation in vacuum-deposited thin-film OLEDs, it is possible to achieve an anisotropic molecular distribution at or near the surface under controlled experimental conditions. In this study, we have used interface-specific vibrational sum frequency generation (VSFG) spectroscopy to determine the orientation of a low-molecular weight OLED material, 4,4'-bis( N -carbazolyl)-1,1'-biphenyl (CBP), at free (air) and buried (CaF 2 ) interfaces. VSFG spectra were measured at four different polarization combinations for five different thicknesses of the CBP film. The spectral shift and VSFG intensity changes with the film thickness can be accurately modeled by considering the optical interference effect of the signals coming from the CBP/air and CBP/CaF 2 interfaces. A global fitting of the experimental spectra for all thicknesses along with theoretical simulations reveal that the long molecular axis of CBP is oriented at an angle of ∼58° (47-70°) from the surface normal at the air/CBP interface, whereas at the CBP/CaF 2 interface, the angle is ∼48° (43-52°). Such a change in the angle (∼10°) suggests that the CBP molecule tends to orient more vertically (edge-on) at the buried CaF 2 interface, which may be attributed to the intermolecular π-π stacking interaction between adjacent CBP molecules.