Andreas Thoman

Dynamics of Imidazolium Ionic Liquids from a Combined Dielectric Relaxation and Optical Kerr Effect Study: Evidence for Mesoscopic Aggregation

We have measured the intermolecular dynamics of the 1,3-dialkylimidazolium-based room-temperature ionic liquids (RTILs) [emim][BF(4)], [emim][DCA], and [bmim][DCA] at 25 degrees C from below 1 GHz to 10 THz by ultrafast optical Kerr effect (OKE) spectroscopy and dielectric relaxation spectroscopy (DRS) augmented by time-domain terahertz and far-infrared FTIR spectroscopy. This concerted approach allows a more detailed analysis to be made of the relatively featureless terahertz region, where the higher frequency diffusional modes are strongly overlapped with librations and intermolecular vibrations. Of greatest interest though, is an intense low frequency (sub-alpha) relaxation that we show is in accordance with recent simulations that have reported mesoscopic structure arising from aggregates or clusters--structure that explains the anomalous and inconveniently high viscosities of these liquids.

Interactions and Dynamics in Ionic Liquids

Precise dielectric spectra have been determined at 25 degrees C over the exceptionally broad frequency range of 0.1 <or= nu/GHz <or= 3000 for the imidazolium-based room-temperature ionic liquids (RTILs) [bmim][BF4], [bmim][PF6], [bmim][DCA], and [hmim][BF4]. The spectra are dominated by a low-frequency process at approximately 1 GHz with a broad relaxation time distribution of the Cole-Davidson or Cole-Cole type, which is thought to correspond to the rotational diffusion of the dipolar cations. In addition, these RTILs possess two Debye relaxations at approximately 5 GHz and approximately 0.6 THz and a damped harmonic oscillation at approximately 2.5 THz. The two higher-frequency modes are almost certainly due to cation librations, but the origin of the approximately 5 GHz mode remains obscure.

Terahertz near-field imaging of electric and magnetic resonances of a planar metamaterial

Experimental investigations of the microscopic electric and in particular the magnetic near-fields in metamaterials remain highly challenging and current studies rely mostly on numerical simulations. Here we report a terahertz near-field imaging approach which provides spatially resolved measurements of the amplitude, phase and polarization of the electric field from which we extract the microscopic magnetic near-field signatures in a planar metamaterial constructed of split-ring resonators (SRRs). In addition to studying the fundamental resonances of an individual double SRR unit we further investigate the interaction with neighboring elements.

Chemical sensing and imaging with pulsed terahertz radiation.

AbstractOver the past decade, terahertz spectroscopy has evolved into a versatile tool for chemically selective sensing and imaging applications. In particular, the potential to coherently generate and detect short, and hence, broadband terahertz pulses led to the development of efficient and compact spectrometers for this interesting part of the electromagnetic spectrum, where common packaging materials are transparent and many chemical compounds show characteristic absorptions. Although early proof-of-principle demonstrations have shown the great potential of terahertz spectroscopy for sensing and imaging, the technology still often lacks the required sensitivity and suffers from its intrinsically poor spatial resolution. In this review we discuss the current potential of terahertz pulse spectroscopy and highlight recent technological advances geared towards both enhancing spectral sensitivity and increasing spatial resolution. Online abstract figureArtists view of a terahertz pulse emitted from a photoconductive antenna probing the vibrational modes of a sugar molecule.

Terahertz Dynamics of Ionic Liquids from a Combined Dielectric Relaxation, Terahertz, and Optical Kerr Effect Study: Evidence for Mesoscopic Aggregation

To exploit the great potential of room-temperature ionic liquids (RTILs) as solvents that offer both low environmental impact and product selectivity, an understanding of the liquid structure, the microscopic dynamics, and the way in which the pertinent macroscopic properties, such as viscosity, thermal conductivity, ionic diffusion, and solvation dynamics depend on these properties, is essential. We have measured the intermolecular dynamics of the 1,3-dialkylimidazoliumbased RTILs [emim][BF4], [emim][DCA], and [bmim][DCA], at 25 °C from below 1 GHz to 10 THz by ultrafast optical Kerr effect (OKE) spectroscopy and dielectric relaxation spectroscopy (DRS) augmented by time-domain terahertz and far-infrared FTIR spectroscopy. This concerted approach allows a more detailed analysis to be made of the relatively featureless terahertz region, where the higher frequency diffusional modes are strongly overlapped with librations and intermolecular vibrations. In the terahertz region, the signal-to-noise ratio of the OKE spectra is particularly high and the data show that there is a greater number of librational and intermolecular vibrational modes than previously detected. Of greatest interest though, is an intense low frequency (sub-alpha) relaxation that we show is in strong accordance with recent simulations that observe mesoscopic structure arising from aggregates or clusters; structure that explains the anomalous and inconveniently-high viscosities of these liquids.

Terahertz-Conductivity of Nano-Structured Gold Films

Terahertz (THz) time-domain spectroscopy is used to measure the complex conductivity of semi-continuous gold films in the spectral region 0.5-2.5 THz. The effects of the characteristic nano-structure of the films on their THz-conductivity are investigated.

Metal-Insulator Phase Transition in VO 2 : A Look from the Far Infrared Side

Vanadium dioxide (VO 2 ) displays a well-known metal-insulator (MI) transition at a temperature of 68°C. In this study we use terahertz time-domain spectroscopy (THz-TDS) to investigate the optical properties of VO 2 thin films in the vicinity of the MI transition temperature in the frequency range 0.1 – 1.5 THz. We observe the interesting effect that the phase of the transmitted THz field through the conducting VO 2 film is delayed in comparison to the phase of the same THz signal transmitted through the insulating VO 2 film. This is in contrast to the expected behavior of a homogeneous, conducting film. This observation shows that even at temperatures significantly above the transition temperature, the formation of a homogeneous, conducting film is incomplete. We demonstrate that effective-medium theory (EMT) in combination with a Drude model accounting for the conductivity of metallic domains formed in the VO 2 film accounts for all our observations. We show that the Maxwell-Garnett EMT is consistent with our observations, whereas the Bruggeman EMT fails to account for our observations.