S. James Allen

Probing the collective vibrational dynamics of a protein in liquid water by terahertz absorption spectroscopy.

Biological polymers are expected to exhibit functionally relevant, global, and subglobal collective modes in the terahertz (THz) frequency range (i.e., picosecond timescale). In an effort to monitor these collective motions, we have experimentally determined the absorption spectrum of solvated bovine serum albumin (BSA) from 0.3 to 3.72 THz (10–124 cm−1). We successfully extract the terahertz molar absorption of the solvated BSA from the much stronger attenuation of water and observe in the solvated protein a dense, overlapping spectrum of vibrational modes that increases monotonically with increasing frequency. We see no evidence of distinct, strong, spectral features, suggesting that no specific collective vibrations dominate the proteins spectrum of motions, consistent with the predictions of molecular dynamics simulations and normal mode analyses of a range of small proteins. The shape of the observed spectrum resembles the ideal quadratic spectral density expected for a disordered ionic solid, indicating that the terahertz normal mode density of the solvated BSA may be modeled, to first order, as that of a three‐dimensional elastic nanoparticle with an aperiodic charge distribution. Nevertheless, there are important detailed departures from that of a disordered inorganic solid or the normal mode densities predicted for several smaller proteins. These departures are presumably the spectral features arising from the unique molecular details of the solvated BSA. The techniques used here and measurements have the potential to experimentally confront theoretical calculations on a frequency scale that is important for macromolecular motions in a biologically relevant water environment.

Electrostatic carrier doping of GdTiO3/SrTiO3 interfaces

Heterostructures and superlattices consisting of a prototype Mott insulator, GdTiO3, and the band insulator SrTiO3 are grown by molecular beam epitaxy and show intrinsic electronic reconstruction, approximately ½ electron per surface unit cell at each GdTiO3/SrTiO3 interface. The sheet carrier densities in all structures containing more than one unit cell of SrTiO3 are independent of layer thicknesses and growth sequences, indicating that the mobile carriers are in a high concentration, two-dimensional electron gas bound to the interface. These carrier densities closely meet the electrostatic requirements for compensating the fixed charge at these polar interfaces. Based on the experimental results, insights into interfacial band alignments, charge distribution, and the influence of different electrostatic boundary conditions are obtained.

Low-dimensional Mott material: Transport in ultrathin epitaxial LaNiO3 films

Electrical resistivity and magnetotransport are explored for thin (3–30 nm), epitaxial LaNiO3 films. Films were grown on three different substrates to obtain LaNiO3 films that are coherently strained, with different signs and magnitude of film strain. It is shown that d-band transport is inhibited as the layers progress from compression to tension. The Hall coefficient is “holelike.” Increasing tensile strain causes the film resistivity to increase, causing strong localization to appear below a critical thickness.

Dielectric spectroscopy of proteins as a quantitative experimental test of computational models of their low-frequency harmonic motions.

Decades of molecular dynamics and normal mode calculations suggest that the largest-scale collective vibrational modes of proteins span the picosecond to nanosecond time scale. Experimental investigation of these harmonic, low-amplitude motions, however, has proven challenging. In response, we have developed a vector network analyzer-based spectrometer that supports the accurate measurement of both the absorbance and refractive index of solvated biomolecules over the corresponding gigahertz to terahertz frequency regime, thus providing experimental information regarding their largest-scale, lowest frequency harmonic motions. We have used this spectrometer to measure the complex dielectric response of lysozyme solutions over the range 65 to 700 GHz and an effective medium model to separate the dielectric response of the solvated protein from that of its buffer. In doing so, we find that each lysozyme is surrounded by a tightly bound layer of 165 ± 15 water molecules that, in terms of their picosecond dynamics, behave as if they are an integral part of the protein. We also find that existing computational descriptions of the proteins dynamics compare poorly with the results of our experiment. Specifically, published normal mode and molecular dynamics simulations do not explain the measured dielectric response unless we introduce a cutoff frequency of 250 GHz below which the density of vibrational modes drops to zero. This cutoff is physically plausible, given the known size of the protein and the known speed of sound in proteins, raising questions as to why it is not apparent in computational models of the proteins motions.

Absorption spectra of liquid water and aqueous buffers between 0.3 and 3.72THz

We have developed a terahertz absorption spectrometer suitable for strongly absorbing liquids such as water, and have precisely measured the absorption spectrum of water between 0.3 and 3.72 THz (10-124 cm(-1)). We have also examined the absorption spectra of aqueous 50 mM potassium phosphate buffers at pH 3 and 8, and find that they do not differ significantly from pure distilled de-ionized water.

Carrier-Controlled Ferromagnetism in SrTiO3

Magnetotransport and superconducting properties are investigated for uniformly La-doped SrTiO3 films and GdTiO3/SrTiO3 heterostructures, respectively. GdTiO3/SrTiO3 interfaces exhibit a high-density two-dimensional electron gas on the SrTiO3-side of the interface, while for the SrTiO3 films carriers are provided by the dopant atoms. Both types of samples exhibit ferromagnetism at low temperatures, as evidenced by a hysteresis in the magnetoresistance. For the uniformly doped SrTiO3 films, the Curie temperature is found to increase with doping and to coexist with superconductivity for carrier concentrations on the high-density side of the superconducting dome. The Curie temperature of the GdTiO3/SrTiO3 heterostructures scales with the thickness of the SrTiO3 quantum well. The results are used to construct a stability diagram for the ferromagnetic and superconducting phases of SrTiO3.

Transport in ferromagnetic GdTiO3 / SrTiO3 heterostructures

Epitaxial GdTiO3/SrTiO3 structures with different SrTiO3 layer thicknesses are grown on (001) (LaAlO3)0.3(Sr2AlTaO6)0.7 substrate surfaces by hybrid molecular beam epitaxy. It is shown that the formation of the pyrochlore (Gd2Ti2O7) phase can be avoided if GdTiO3 is grown by shuttered growth, supplying alternating monolayer doses of Gd and of the metalorganic precursor that supplies both Ti and O. Phase-pure GdTiO3 films grown by this approach exhibit magnetic ordering with a Curie temperature of 30 K. The electrical transport characteristics can be understood as being dominated by a conductive interface layer within the SrTiO3.

Enhancing the electron mobility of SrTiO3 with strain

We demonstrate, using high-mobility SrTiO3 thin films grown by molecular beam epitaxy, that stress has a pronounced influence on the electron mobility in this prototype complex oxide. Moderate strains result in more than 300% increases in the electron mobilities with values exceeding 120 000 cm2/V s and no apparent saturation in the mobility gains. The results point to a range of opportunities to tailor high-mobility oxide heterostructure properties and open up ways to explore oxide physics.

A heterojunction modulation-doped Mott transistor

A heterojunction Mott field effect transistor (FET) is proposed that consists of an epitaxial channel material that exhibits an electron correlation induced Mott metal-to-insulator transition. The Mott material is remotely (modulation) doped with a degenerately doped conventional band insulator. An applied voltage modulates the electron transfer from the doped band insulator to the Mott material and produces transistor action by inducing an insulator-to-metal transition. Materials parameters from rare-earth nickelates and SrTiO3 are used to assess the potential of the “modulation-doped Mott FET” (ModMottFET or MMFET) as a next-generation switch. It is shown that the MMFET is characterized by unique “charge gain” characteristics as well as competitive transconductance, small signal gain, and current drive.

High-precision gigahertz-to-terahertz spectroscopy of aqueous salt solutions as a probe of the femtosecond-to-picosecond dynamics of liquid water

Because it is sensitive to fluctuations occurring over femtoseconds to picoseconds, gigahertz-to-terahertz dielectric relaxation spectroscopy can provide a valuable window into waters most rapid intermolecular motions. In response, we have built a vector network analyzer dielectric spectrometer capable of measuring absorbance and index of refraction in this frequency regime with unprecedented precision. Using this to determine the complex dielectric response of water and aqueous salt solutions from 5.9 GHz to 1.12 THz (which we provide in the supplementary material), we have obtained strong new constraints on theories of waters collective dynamics. For example, while the salt-dependencies we observe for waters two slower relaxations (8 and 1 ps) are easily reconciled with suggestions that they arise due to rotations of fully and partially hydrogen bonded molecules, respectively, the salt-dependence of the fastest relaxation (180 fs) appears difficult to reconcile with its prior assignment to liberations of single hydrogen bonds.