Charles A. Schmuttenmaer

Exciton-like trap states limit electron mobility in TiO2 nanotubes

Nanoparticle films have become a promising low-cost, high-surface-area electrode material for solar cells and solar fuel production. Compared to sintered nanoparticle films, oriented polycrystalline titania nanotubes offer the advantage of directed electron transport, and are expected to have higher electron mobility. However, macroscopic measurements have revealed their electron mobility to be as low as that of nanoparticle films. Here, we show, through time-resolved terahertz spectroscopy, that low mobility in polycrystalline TiO(2) nanotubes is not due to scattering from grain boundaries or disorder-induced localization as in other nanomaterials, but instead results from a single sharp resonance arising from exciton-like trap states. If the number of these states can be lowered, this could lead to improved electron transport in titania nanotubes and significantly better solar cell performance.

A visible light water-splitting cell with a photoanode formed by codeposition of a high-potential porphyrin and an iridium water-oxidation catalyst

A high-potential porphyrin is codeposited on TiO2 nanoparticles together with our Cp*–iridium water-oxidation catalyst to give a photoanode for a water-splitting cell. The photoanode optically resembles the porphyrin yet electrochemically responds like the Ir catalyst when it is immersed in aqueous solutions. Photoelectrochemical data show that illumination of the codeposited anode in water results in a marked enhancement and stability of the photocurrent, providing evidence for light-induced activation of the catalyst.

Spectroscopy and dynamics of mixtures of water with acetone, acetonitrile, and methanol

3t o 55 cm 21 , and from 400 to 1200 cm 21 . The far-infrared absorption of the mixtures is substantially less than that for ideal mixtures, and Debye time constants calculated from the spectra are longer for the real than for the ideal mixtures. Significant composition dependence is observed in the high frequency librational spectra of the mixtures, and is reproduced by the MD simulations. Single dipole and angular velocity spectra are also reported, as are detailed changes in the hydrogen bonding environment in the mixtures. There is a loss of tetrahedral water structure on mixing, yet water molecules have a strong tendency to aggregate, especially in the acetone and acetonitrile mixtures. Spatial distribution functions are reported for the acetone/water system.

Subpicosecond carrier dynamics in low-temperature grown GaAs as measured by time-resolved terahertz spectroscopy

The transient photoconductivity in a 1 μm layer of low temperature grown GaAs (LT-GaAs) on a GaAs substrate was measured using time-resolved terahertz spectroscopy. When photoexcitation occurs at 400 nm we find a time-dependent mobility that increases from 400±100 to 1100±100 cm2 V−1 s−1 with a time constant of 2 ps. Photoexcitation at 800 nm produces a time-independent mobility of 3000±500 cm2 V−1 s−1. We determine the carrier lifetime in LT-GaAs to be 1.1 ± 0.1 ps.

A molecular catalyst for water oxidation that binds to metal oxide surfaces

Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts.

Facet-Dependent Photoelectrochemical Performance of TiO2 Nanostructures: An Experimental and Computational Study

The behavior of crystalline nanoparticles depends strongly on which facets are exposed. Some facets are more active than others, but it is difficult to selectively isolate particular facets. This study provides fundamental insights into photocatalytic and photoelectrochemical performance of three types of TiO(2) nanoparticles with predominantly exposed {101}, {010}, or {001} facets, where 86-99% of the surface area is the desired facet. Photodegradation of methyl orange reveals that {001}-TiO(2) has 1.79 and 3.22 times higher photocatalytic activity than {010} and {101}-TiO(2), respectively. This suggests that the photochemical performance is highly correlated with the surface energy and the number of under-coordinated surface atoms. In contrast, the photoelectrochemical performance of the faceted TiO(2) nanoparticles sensitized with the commercially available MK-2 dye was highest with {010}-TiO(2) which yielded an overall cell efficiency of 6.1%, compared to 3.2% for {101}-TiO(2) and 2.6% for {001}-TiO(2) prepared under analogous conditions. Measurement of desorption kinetics and accompanying computational modeling suggests a stronger covalent interaction of the dye with the {010} and {101} facets compared with the {001} facet. Time-resolved THz spectroscopy and transient absorption spectroscopy measure faster electron injection dynamics when MK-2 is bound to {010} compared to other facets, consistent with extensive computational simulations which indicate that the {010} facet provides the most efficient and direct pathway for interfacial electron transfer. Our experimental and computational results establish for the first time that photoelectrochemical performance is dependent upon the binding energy of the dye as well as the crystalline structure of the facet, as opposed to surface energy alone.

Coherent terahertz emission from ferromagnetic films excited by femtosecond laser pulses

It is shown that the laser induced ultrafast demagnetization of ferromagnetic films results in the emission of a terahertz electromagnetic pulse. This emission has been detected from Ni films using free-space electro-optic sampling. The radiated electric field E(t) is explained by Maxwell equations (radiation from a time dependent magnetic dipole), and is expected to be proportional to the second time derivative of the magnetization d2M/dt2, as measured in the far field. This technique opens appealing perspectives in the context of measuring and understanding the ultrafast spin dynamics as well as the interaction of electrons (both charge and spin) with electromagnetic fields.

Far-infrared spectra and associated dynamics in acetonitrile-water mixtures measured with femtosecond THz pulse spectroscopy

We report the frequency-dependent absorption coefficient and index of refraction in the far-infrared region of the spectrum for mixtures of acetonitrile and water. The mixtures do not behave ideally, and deviate from ideality most noticeably for mixtures that are between 25% and 65% acetonitrile by volume. Two implementations of the Debye model for describing the dielectric relaxation behavior of mixtures are compared, and we show that these mixtures are better treated as uniform solutions rather than as two-component systems. We find an enhanced structure in the mixtures, relative to ideal mixtures, but we do not find direct evidence for microheterogeneity. The Debye time constant for the primary relaxation process for the mixtures is up to 25% longer than that for an ideal mixture.

Rotational spectra and structures of the Ar2–H/DF trimers

The feasibility of studying weakly bound, neutral van der Waals clusters through their microwave rotational spectra has been shown by identifying and characterizing Ar2–H/DF. Detection of the trimeric complexes was accomplished with the Flygare Mark II Fourier transform spectrometer, modified to better utilize its inherent sensitivity. Twenty‐six b‐dipole transitions (all ee↔oo) were observed in the 3–18 GHz region for Ar2–HF, and 19 for Ar2–DF, and their hyperfine structure analyzed. Fitting of the line centers with Kirchhoff’s NBS program gave values (all in MHz) for Watson’s determinable parameters of 3576.508(1), 1739.139(1), and 1161.054(1) for the rotational constants A‘, B‘, and C‘ in Ar2–HF, and of 3506.791(1), 1744.056(1), and 1155.636(1) in Ar2–DF. The centrifugal distortion constants τ1, τ2, τaaaa, τbbbb, and τcccc were found to be −0.2039(3), −0.0522(1), −0.5353(5), −0.1159(1), and −0.02021(1) in Ar2–HF, and −0.2116(7), −0.0528(2), −0.4941(7), −0.1123(1), and −0.0191(1) in Ar2–DF. Three small ...

Observation of surface enhanced multiphoton photoemission from metal surfaces in the short pulse limit

Photoelectrons with excess kinetic energy corresponding to several absorbed photons above the work function have been measured from atomically clean Cu(110) and Cu(100) surfaces under ultrahigh vacuum conditions. The power dependence of the photoemission yield does not follow a simple power law dependence corresponding to the number of photons absorbed. This behavior is reminiscent of other above threshold ionization (ATI) or tunnel ionization (TI) processes observed for atoms in the gas phase. The photoelectrons are generated with laser pulsewidths less than 100 fs in duration and peak powers as low as 100 MW/cm2. These intensities are on the order of 105 times lower than that required to observe similar phenomena in the gas phase. The relatively low intensities and correlation with surface roughness suggests a contribution from a surface enhancement mechanism. Thermal heating and space charge effects have been ruled out, and the possibility of electric field enhancement at the surface due to the couplin...