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Molecular liquids have long been known to undergo various distinct intermolecular motions, from fast librations and cage-rattling oscillations to slow orientational and translational diffusion. However, their resultant gigahertz to terahertz spectra are far from simple, appearing as broad shapeless bands that span many orders of magnitude of frequency, making meaningful interpretation troublesome. Ad hoc spectral line shape fitting has become a notoriously fine art in the field; a unified approach to handling such spectra is long overdue. Here we apply ultrafast optical Kerr-effect (OKE) spectroscopy to study the intermolecular dynamics of room-temperature n-alkanes, cycloalkanes, and six-carbon rings, as well as liquid methane and propane. This work provides stress tests and converges upon an experimentally robust model across simple molecular series and range of temperatures, providing a blueprint for the interpretation of the dynamics of van der Waals liquids. This will enable the interpretation of low-frequency spectra of more complex liquids.

Low-frequency vibrations play an essential role in biomolecular processes involving DNA such as gene expression, charge transfer, drug intercalation, and DNA–protein recognition. However, understanding of the vibrational basis of these mechanisms relies on theoretical models due to the lack of experimental evidence. Here we present the low-frequency vibrational spectra of G-quadruplexes (structures formed by four strands of DNA) and B-DNA characterized using femtosecond optical Kerr-effect spectroscopy. Contrary to expectation, we found that G-quadruplexes show several strongly underdamped delocalized phonon-like modes that have the potential to contribute to the biology of the DNA at the atomic level. In addition, G-quadruplexes present modes at a higher frequency than B-DNA demonstrating that changes in the stiffness of the molecule alter its gigahertz to terahertz vibrational profile. These results demonstrate that current theoretical models fail to predict basic properties of the vibrational modes of DNA.Statement of significanceA number of recent studies have identified thermally excited low-frequency vibrational modes as a key deciding factor in the biological function of DNA. However, the nature of these vibrational modes has never been established. Here, vibrational spectroscopy with unrivalled signal-to-noise in the gigahertz to terahertz range is used to determine the low-frequency Raman spectra of nucleotides and oligomeric DNAs carefully chosen to form G-quadruplexes, structures formed by four strands of DNA common in the genome. These G-quadruplexes exhibit an unusual group of highly-underdamped delocalized vibrational modes—not reproduced by any of the theoretical models in use—which are expected to be the thermally excited. This provides a new perspective on the role of low-frequency vibrational modes in protein interactions and allostery.

Water dynamics in the solvation shell of solutes plays a very important role in the interaction of biomolecules and in chemical reaction dynamics. However, a selective spectroscopic study of the solvation shell is difficult because of the interference of the solute dynamics. Here we report on the observation of heavily slowed down water dynamics in the solvation shell of different solutes by measuring the low-frequency spectrum of solvation water, free from the contribution of the solute. A slowdown factor of ∼50 is observed even for relatively low concentrations of the solute. We go on to show that the effect can be generalized to different solutes including proteins.

We show that surface plasmons, excited with femtosecond laser pulses on continuous or discontinuous gold substrates, strongly enhance the generation and emission of ultrashort, broadband terahertz pulses from single layer graphene. Without surface plasmon excitation, for graphene on glass, 'nonresonant laser-pulse-induced photon drag currents' appear to be responsible for the relatively weak emission of both s- and p-polarized terahertz pulses. For graphene on a discontinuous layer of gold, only the emission of the p-polarized terahertz electric field is enhanced, whereas the s-polarized component remains largely unaffected, suggesting the presence of an additional terahertz generation mechanism. We argue that in the latter case, 'surface-plasmon-enhanced optical rectification', made possible by the lack of inversion symmetry at the graphene on gold surface, is responsible for the strongly enhanced emission. The enhancement occurs because the electric field of surface plasmons is localized and enhanced where the graphene is located: at the surface of the metal. We believe that our results point the way to small, thin, and more efficient terahertz photonic devices.

We show that the interface between gold and thermally formed cuprous oxide, which emits terahertz radiation when illuminated with ultrafast femtosecond lasers, is in fact an AuCu/Cu2O interface due to the formation of the thermal diffusion alloy AuCu. The alloy enables the formation of a Schottky-barrier-like electric field near the interface which is essential to explain the THz emission from these samples. We confirm the formation of this AuCu layer by x-ray diffraction measurements, ellipsometry, and visual inspection. We determined the frequency-dependent complex refractive indices of the Cu2O and AuCu layer and verified them using reflection spectroscopy measurements. These refractive indices can be used for optimizing the thickness of Cu2O for maximum THz emission from these interfaces.

Terahertz emission by ultrafast laser excitation of semiconductors is done conventionally in bulk wafers or thin films thicker than the optical penetration depth. Here we present counter-intuitive-results where enhanced terahertz emission is made possible by using ultrathin films of semiconductors.

We report on the surprisingly strong, broadband emission of coherent terahertz pulses from ultrathin layers of semiconductors such as amorphous silicon, germanium and polycrystalline cuprous oxide deposited on gold, upon illumination with femtosecond laser pulses. The strength of the emission is surprising because the materials are considered to be bad (amorphous silicon and polycrystalline cuprous oxide) or fair (amorphous germanium) terahertz emitters at best. We show that the strength of the emission is partly explained by cavity-enhanced optical absorption. This forces most of the light to be absorbed in the depletion region of the semiconductor/metal interface where terahertz generation occurs. For an excitation wavelength of 800 nm, the strongest terahertz emission is found for a 25 nm thick layer of amorphous germanium, a 40 nm thick layer of amorphous silicon and a 420 nm thick layer of cuprous oxide, all on gold. The emission from cuprous oxide is similar in strength to that obtained with optical rectification from a 300 μm thick gallium phosphide crystal. As an application of our findings we demonstrate how such thin films can be used to turn standard optical components, such as paraboloidal mirrors, into self-focusing terahertz emitters. © 2013 Optical Society of America.

Electromagnetic wave emission based on optical rectification at terahertz (THz) wavelengths was observed from surface-immobilized gold nanospheres (SIGNs) above a gold surface. Although the excitation wavelength is off-resonant with the localized surface plasmons, the THz emission field was observed to be approximately 4.8 times greater than that from a percolated gold thin film of 10 nm thickness. A theoretical calculation predicts that the light electric field is enhanced in the SIGN system, even at off-resonance wavelengths. The observed THz field amplitude was quadratic with the illumination light field, suggesting that the THz generation is due to a second-order nonlinear optical process.

Emission of terahertz radiation is observed when a single layer graphene on a glass slide is excited with femtosecond near-infrared laser pulses. Furthermore, we can enhance the amplitude of terahertz emission by surface plasmon resonance excitation on a thin gold film in the Kretschmann geometry.

Terahertz (THz) transmission spectroscopy is used to measure the oxidation kinetics of copper thin films evaporated on silicon substrates. The transmission of broadband THz pulses from 1 to 7 THz through the copper film is measured while it gets oxidized at an elevated temperature in ambient air. The change in the transmitted THz electric field is correlated with the growth of the cuprous oxide layer and the decrease in thickness of the copper layer. Oxidation curves were obtained for heating temperatures of 120–150?°C and were found to follow a parabolic rate law. Using the Arrhenius equation, we calculate an activation energy for diffusion of 0.55?eV. By measuring the THz transmission through unoxidized copper layers of several thicknesses, we also measured the optical properties of thin copper films around the percolation threshold thickness of 7?nm. Around the percolation transition, the optical properties of freshly deposited copper thin films are very different from that of copper layers of the same thickness remaining after partial oxidation of thick copper films.

Emission of terahertz radiation is observed when surface plasmons are excited on a thin film of gold, in the Kretschmann geometry. When a hemicyanine-terminated alkanethiol self-assembled monolayer of thickness 1.2 nm is deposited on the gold film, stronger terahertz emission is observed. Our experimental results confirm that enhanced terahertz emission is possible from planar gold surfaces when surface plasmons are excited.

Emission of terahertz radiation is observed when semi-continuous ultrathin gold films near the percolation threshold are excited with femtosecond near-infrared laser pulses. Our experimental results suggest that the emission is through a percolation-enhanced second-order nonlinear optical rectification process.

Subpicosecond terahertz pulses are generated from the surfaces of graphite samples, when illuminated with femtosecond near-infrared laser pulses. Our experiments with highly oriented pyrolytic graphite samples suggest that the emission of THz radiation is caused by photoinduced transient charge carrier movements along the c-axis of the crystal. This is further confirmed by studying the effects of an in-plane magnetic-field which deflects the photocurrent and thereby changes the THz polarization. The experimental results point to two possible generation mechanisms, carrier acceleration in the space charge layer near the graphite surface and/or the photo-Dember effect.

Generation of subpicosecond terahertz pulses is observed when graphite surfaces are illuminated with femtosecond near-infrared laser pulses. The nonlinear optical generation of THz pulses from graphite is unexpected since, in principle, the material possesses a centre of inversion symmetry. Experiments with highly oriented pyrolytic graphite crystals suggest that the THz radiation is generated by a transient photocurrent in a direction normal to the graphene planes, along the c-axis of the crystal. This is supported by magnetic-field induced changes in the THz electric-field polarization, and consequently, the direction of the photocurrent. We show that other forms of graphite, such as a pencil drawing on paper, are also capable of emitting THz pulses.

When (nanostructured) metals, such as gold and silver, are illuminated with laser pulses having a duration in the femtosecond range, they can emit pulses of THz light. Most of these experiments have been performed using amplified lasers, giving rise to energy densities on the sample on the order of mJ cm−2. The results of the different experiments are surprisingly inconsistent in both the measurements of the THz fluence as a function of laser fluence and in the interpretation of the results. This paper reviews the current state of affairs of this interesting topic and discusses some effects related to surface preparation that may influence the emission THz light on metals, particularly silver and copper. We also show results of measurements on nanostructured metals using unamplified laser pulses, which emphasize the role played by plasmons in the generation of THz light. When increasing the optical energy density on a specially nanostructured sample, we observe a transition from a 'classical' second-order non-linear optical process to a higher-order process as the source of the THz radiation. This supports recent results on a differently structured metal by Polyushkin et al (2014 Phys. Rev. B 89 125426), who also observe two different power regimes when decreasing the intensity coming from the high energy density side.

Terahertz emission by ultrafast optical excitation of semiconductor/metal interfaces strongly depends on the strength of the depletion-field. Here, we report on the strong enhancement of the emission after optical excitation of surface plasmons at these interfaces. The enhancement is caused by the plasmonic localization of the pump light near the metal surface, where the depletion-field is the strongest. Compared to the case where no surface plasmons are excited, a terahertz field enhancement of more than an order of magnitude is obtained for a particular thickness of cuprous oxide layer on gold, where localized surface plasmons are excited at the interface.

Low-frequency vibrations play an essential role in biomolecular processes involving DNA such as gene expression, charge transfer, drug intercalation, and DNA–protein recognition. However, understanding the vibrational basis of these mechanisms relies on theoretical models due to the lack of experimental evidence. Here we present the low-frequency vibrational spectra of G-quadruplexes (structures formed by four strands of DNA) and B-DNA characterized using femtosecond optical Kerr-effect spectroscopy. Contrary to expectation, we found that G-quadruplexes show several strongly underdamped delocalized phonon-like modes that have the potential to contribute to the biology of the DNA at the atomic level. In addition, G-quadruplexes present modes at a higher frequency than B-DNA demonstrating that changes in the stiffness of the molecule alter its gigahertz to terahertz vibrational profile., Low-frequency vibrations play an essential role in biomolecular processes involving DNA such as gene expression, charge transfer, drug intercalation, and DNA–protein recognition.