Reaction pathways of biochemical processes are influenced by the dissipative electrostatic interaction of the reagents with solvent water molecules. The simulation of these interactions requires a parametrization of the permanent and induced dipole moments. However, the underlying molecular polarizability of water and its dependence on ions are partially unknown. Here, we apply intense terahertz pulses to liquid water, whose oscillations match the timescale of orientational relaxation. Using a combination of terahertz pump / optical probe experiments, molecular dynamics simulations, and a Langevin dynamics model, we demonstrate a transient orientation of their dipole moments, not possible by optical excitation. The resulting birefringence reveals that the polarizability of water is lower along its dipole moment than the average value perpendicular to it. This anisotropy, also observed in heavy water and alcohols, increases with the concentration of sodium iodide dissolved in water. Our results enable a more accurate parametrization and a benchmarking of existing and future water models.

X-ray crystallography is one of the main methods to determine atomic-resolution 3D images of the whole spectrum of molecules ranging from small inorganic clusters to large protein complexes consisting of hundred-thousands of atoms that constitute the macromolecular machinery of life. Life is not static, and unravelling the structure and dynamics of the most important reactions in chemistry and biology is essential to uncover their mechanism. Many of these reactions, including photosynthesis which drives our biosphere, are light induced and occur on ultrafast timescales. These have been studied with high time resolution primarily by optical spectroscopy, enabled by ultrafast laser technology, but they reduce the vast complexity of the process to a few reaction coordinates. In the AXSIS project at CFEL in Hamburg, funded by the European Research Council, we develop the new method of attosecond serial X-ray crystallography and spectroscopy, to give a full description of ultrafast processes atomically resolved in real space and on the electronic energy landscape, from co-measurement of X-ray and optical spectra, and X-ray diffraction. This technique will revolutionize our understanding of structure and function at the atomic and molecular level and thereby unravel fundamental processes in chemistry and biology like energy conversion processes. For that purpose, we develop a compact, fully coherent, THz-driven atto-second X-ray source based on coherent inverse Compton scattering off a free-electron crystal, to outrun radiation damage effects due to the necessary high X-ray irradiance required to acquire diffraction signals. This highly synergistic project starts from a completely clean slate rather than conforming to the specifications of a large free-electron laser (FEL) user facility, to optimize the entire instrumentation towards fundamental measurements of the mechanism of light absorption and excitation energy transfer. A multidisciplinary team formed by laser-, accelerator,- X-ray scientists as well as spectroscopists and biochemists optimizes X-ray pulse parameters, in tandem with sample delivery, crystal size, and advanced X-ray detectors. Ultimately, the new capability, attosecond serial X-ray crystallography and spectroscopy, will be applied to one of the most important problems in structural biology, which is to elucidate the dynamics of light reactions, electron transfer and protein structure in photosynthesis.

Highly-efficient optical generation of narrowband terahertz radiation enables unexplored technologies and sciences from compact electron acceleration to charge manipulation in solids. State-of-the-art conversion efficiencies are currently achieved using difference-frequency generation driven by temporal beating of chirped pulses but remain, however, far lower than desired or predicted. Here we show that high-order spectral phase fundamentally limits the efficiency of narrowband difference-frequency generation using chirped-pulse beating and resolve this limitation by introducing a novel technique based on tuning the relative spectral phase of the pulses. For optical terahertz generation, we demonstrate a 13-fold enhancement in conversion efficiency for 1%-bandwidth, 0.361 THz pulses, yielding a record energy of 0.6 mJ and exceeding previous optically-generated energies by over an order of magnitude. Our results prove the feasibility of millijoule-scale applications like terahertz-based electron accelerators and light sources and solve the long-standing problem of temporal irregularities in the pulse trains generated by interfering chirped pulses.

Optical rectification with tilted pulse fronts in lithium niobate crystals is one of the most promising methods to generate terahertz (THz) radiation. In order to achieve higher optical-to-THz energy efficiency, it is necessary to cryogenically cool the crystal not only to decrease the linear phonon absorption for the generated THz wave but also to lengthen the effective interaction length between infrared pump pulses and THz waves. However, the refractive index of lithium niobate crystal at lower temperature is not the same as that at room temperature, resulting in the necessity to re-optimize or even re-build the tilted pulse front setup. Here, we performed a temperature dependent measurement of refractive index and absorption coefficient on a 6.0 mol% MgO-doped congruent lithium niobate wafer by using a THz time-domain spectrometer (THz-TDS). When the crystal temperature was decreased from 300 K to 50 K, the refractive index of the crystal in the extraordinary polarization decreased from 5.05 to 4.88 at 0.4 THz, resulting in ~1° change for the tilt angle inside the lithium niobate crystal. The angle of incidence on the grating for the tilted pulse front setup at 1030 nm with demagnification factor of −0.5 needs to be changed by 3°. The absorption coefficient decreased by 60% at 0.4 THz. These results are crucial for designing an optimum tilted pulse front setup based on lithium niobate crystals.

We generate narrowband terahertz (THz) radiation in periodically poled lithium niobate (PPLN) crystals using two chirped-and-delayed driver pulses from a high-energy Ti:sapphire laser. The generated frequency is determined by the phase-matching condition in the PPLN and influences the temporal delay of the two pulses for efficient terahertz generation. We achieve internal conversion efficiencies up to 0.13% as well as a record multicycle THz energy of 40 μJ at 0.544 THz in a cryogenically cooled PPLN.

We experimentally investigate the limits to 800 nm-to-terahertz (THz) energy conversion in lithium niobate at room temperature driven by amplified Ti:Sapphire laser pulses with tilted-pulse-front. The influence of the pump central wavelength, pulse duration, and fluence on THz generation is studied. We achieved a high peak efficiency of 0.12% using transform limited 150 fs pulses and observed saturation of the optical to THz conversion efficiency at a fluence of 15 mJ/cm 2 . We experimentally identify two main limitations for the scaling of optical-to-THz conversion efficiencies: (i) the large spectral broadening of the optical pump spectrum in combination with large angular dispersion of the tilted-pulse-front and (ii) free-carrier absorption of THz radiation due to multi-photon absorption of the 800 nm radiation. Strong-field terahertz (THz) sources hold promise for enabling myriads of novel applications. They possess intense electric and magnetic fields at frequencies which are particularly amenable to studies of condensed matter dynamics [1][2][3], manipulation of molecules [4], highharmonic generation (HHG) [5], and compact chargedparticle acceleration [6][7], among others. Therefore, there is a great need for the development of robust and efficient strong-field THz sources.These sources are predominantly accelerator-based facilities (delivering up to 100 µJ THz energy) [8,9] or ultrafast laser-based table-top systems [10]. Laboratory scale systems are of particular interest due to accessibility and relatively low cost. In this category, laser-induced air/gas plasmas (delivering up to 5 µJ THz energy) [11] and optical rectification (OR) of infrared (IR) pulses in nonlinear optical crystals (delivering up to 0.4 mJ THz energy) [12] have emerged as the most common methods of all THz generation modalities. The highest optical-toTHz conversion efficiencies (henceforth referred to as conversion efficiency) in excess of 1% at room temperature have been achieved by OR employing angularly dispersed femtosecond IR pump pulses in lithium niobate [13,14]. As a result, these systems are especially relevant to generating mJ-level THz pulses [12]. In this approach, angular dispersion is introduced to compensate for the large difference in refractive indices between IR and THz frequencies by forming a tilted-pulse-front. The generated THz then propagates perpendicular to this tilted-pulsefront and phase matching is achieved in a non-collinear configuration. OR systems based on lithium niobate are powered predominantly by sources in the 1 µm and 800 nm wavelength regions. While the former yields much higher conversion efficiencies, today, 800 nm sources based on Ti:Sapphire systems prevail in ultrafast laser technology as the most accessible and widely employed sources. Consequently, exploring the limits to achievable conversion efficiency is a great value in the pursuit of accessible high-energy THz sources.In this paper we extensively investigate the limits of conversion efficiency with 800 nm systems through a systemati...

We investigate a regime of parametric amplification in which the pump and signal waves are spectrally separated by only a few hundreds of GHz frequency - therefore resulting in a sub-THz frequency idler wave. Operating in this regime we find an optical parametric amplifier (OPA) behavior which is highly dissimilar to conventional OPAs. In this regime, we observe multiple three-wave mixing processes occurring simultaneously which results in spectral cascading around the pump and signal wave. Via numerical simulations, we elucidate the processes at work and show that cascaded optical parametric amplification offers a pathway toward THz-wave generation beyond the Manly-Rowe limit and toward the generation of high-energy, sparse frequency-combs.

The generation of high-energy narrowband terahertz radiation has gained heightened importance in recent years due to its potentially transformative impact on spectroscopy, high-resolution radar and more recently electron acceleration. Among various applications, such terahertz radiation is particularly important for table-top free electron lasers, which are at the moment a subject of extensive research. Second-order nonlinear optical methods are among the most promising techniques to achieve the required coherent radiation with energy >10 mJ, peak field >100 MV/m, and frequency between 0.1 and 1 THz. However, they are conventionally thought to suffer from low efficiencies <~10 -3 , due to the high ratio between optical and terahertz photon energies, in what is known as the Manley-Rowe limitation. In this paper, we review the current second-order nonlinear optical methods for the generation of narrowband terahertz radiation. We explain how to employ spectral cascading to increase the efficiency beyond the Manley-Rowe limit and describe the first experimental results in the direction of a terahertz-cascaded optical parametric amplifier, a novel technique which promises to fully exploit spectral cascading to generate narrowband terahertz radiation with few percent optical-to-terahertz conversion efficiency. _____________