Ultrafast terahertz Stark spectroscopy reveals the excited-state dipole moments of retinal in bacteriorhodopsin.

The photoinduced all-trans to 13-cis isomerization of the retinal Schiff base represents the ultrafast first step in the reaction cycle of bacteriorhodopsin (BR). Extensive experimental and theoretical work has addressed excited-state dynamics and isomerization via a conical intersection with the ground state. In conflicting molecular pictures, the excited state potential energy surface has been modeled as a pure S[Formula: see text] state that intersects with the ground state, or in a 3-state picture involving the S[Formula: see text] and S[Formula: see text] states. Here, the photoexcited system passes two crossing regions to return to the ground state. The electric dipole moment of the Schiff base in the S[Formula: see text] and S[Formula: see text] state differs strongly and, thus, its measurement allows for assessing the character of the excited-state potential. We apply the method of ultrafast terahertz (THz) Stark spectroscopy to measure electric dipole changes of wild-type BR and a BR D85T mutant upon electronic excitation. A fully reversible transient broadening and spectral shift of electronic absorption is induced by a picosecond THz field of several megavolts/cm and mapped by a 120-fs optical probe pulse. For both BR variants, we derive a moderate electric dipole change of 5 [Formula: see text] 1 Debye, which is markedly smaller than predicted for a neat S[Formula: see text]-character of the excited state. In contrast, S[Formula: see text]-admixture and temporal averaging of excited-state dynamics over the probe pulse duration gives a dipole change in line with experiment. Our results support a picture of electronic and nuclear dynamics governed by the interaction of S[Formula: see text] and S[Formula: see text] states in a 3-state model.

Hydration structure and dynamics of phosphoric acid and its anions-Ultrafast 2D-IR spectroscopy and ab initio molecular dynamics simulations.

The hydration shells of phosphate ions and phosphate groups of nucleotides and phospholipid membranes display markedly different structures and hydrogen-bond strengths. Understanding phosphate hydration requires insight into the spatial arrangements of water molecules around phosphates and in thermally activated structure fluctuations on ultrafast time scales. Femtosecond two-dimensional infrared spectroscopy of phosphate vibrations, particularly asymmetric stretching vibrations between 1000 and 1200 cm-1, and ab initio molecular dynamics (AIMD) simulations are combined to map and characterize dynamic local hydration structures and phosphate-water interactions. Phosphoric acid H3PO4 and its anions H2PO4-, HPO42-, and PO43- are studied in aqueous environments of different pH value. The hydration shells of phosphates providing OH donor groups in hydrogen bonds with the first water layer undergo ultrafast structural fluctuations, which induce a pronounced spectral diffusion of vibrational excitations on a sub-300 fs time scale. With a decreasing number of phosphate OH groups, the hydration shell becomes more ordered and rigid. The 2D-IR line shapes observed with hydrated PO43- ions display a pronounced inhomogeneous broadening, reflecting a distribution of hydration geometries without fast equilibration. The AIMD simulations allow for an in-depth characterization of the hydration geometries with different numbers of water molecules in the first hydration layer and different correlation functions of the fluctuating electric field that the water environment exerts on the vibrational phosphate oscillators.

Nonlinear Terahertz Polarizability of Electrons Solvated in a Polar Liquid.

The nonlinear polaronic response of electrons solvated in liquid 2-propanol is studied by two-dimensional terahertz spectroscopy. Solvated electrons with a concentration of c_{e}≈800 µM are generated by femtosecond photoionization of alcohol molecules. Electron relaxation to a localized ground state impulsively excites coherent polaron oscillations with a frequency of 3.9 THz. Off-resonant perturbation of the terahertz coherence by a pulse centered at 1.5 THz modifies the polaron oscillation phase. This nonlinear change of electron polarizability is reproduced by theoretical calculations.

Cr:ZnS-based soliton self-frequency shifted signal generation for a tunable sub-100 fs MWIR OPCPA.

We present a tunable, high-energy optical parametric chirped pulse amplification system with a front-end based on a femtosecond Cr:ZnS laser. By taking advantage of the broad emission spectrum of the femtosecond Cr:ZnS master oscillator, we are able to directly seed the holmium-based pump around 2 µm. At the same time, the signal pulses for the parametric process are generated via Raman self-frequency shifting of the red end of the spectrum centered at 2.4 µm. The solitons, generated in a fluoride fiber, are tunable over the wavelength range between 2.8 and 3.2 µm. The optical parametric amplifier operates at a 1 kHz repetition rate, and consists of two stages equipped with ZGP as nonlinear crystal. The generated idler pulses are tunable between 5.4 and 6.8 µm with a pulse energy of up to 400 µJ. Dispersion management using bulk material stretching and compression in combination with precise phase shaping prior to amplification enables idler pulses of a sub-100 fs duration, translating into a peak power as high as 4 GW.

Kinetics of excitation transfer from Cr2+ to Fe2+ ions in co-doped ZnSe.

The transfer of electronic excitations from Cr2+ to Fe2+ ions in co-doped epitaxially grown ZnSe is studied by time-resolved photoluminescence (PL) spectroscopy with unprecedented sub-10 ns time resolution. Upon excitation of Cr2+ ions by a picosecond pulse at 2.05 µm wavelength, PL from Fe2+ ions displays a delayed onset and a retarded decay in comparison to Fe2+ PL directly excited at 3.24 µm. We measure an extremely rapid 60 ns buildup of the Fe2+ luminescence, which is followed by a slower relaxation on the few micrometer scale. The experimental results are analyzed in the framework of Förster radiationless resonant energy transfer. Directly connecting to the work of Fedorov et al. [Opt. Mater. Express9, 2340 (2019)10.1364/OME.9.002340], the 60-ns buildup time of energy transfer is found to correspond to a Cr2+-Fe2+ distance of 0.95 nm, close to the length of the space diagonal of the ZnSe unit cell. This result demonstrates a significant density of spatially correlated Cr2+-Fe2+ ion pairs at short distance, in parallel to ions with a random distribution at a larger mutual separation.

Phonon-Induced Relocation of Valence Charge in Boron Nitride Observed by Ultrafast X-Ray Diffraction.

The impact of coherent phonon excitations on the valence charge distribution in cubic boron nitride is mapped by femtosecond x-ray powder diffraction. Zone-edge transverse acoustic (TA) two-phonon excitations generated by an impulsive Raman process induce a steplike increase of diffracted x-ray intensity. Charge density maps derived from transient diffraction patterns reveal a spatial transfer of valence charge from the interstitial region onto boron and nitrogen atoms. This transfer is modulated with a frequency of 250 GHz due to a coherent superposition of TA phonons related to the ^{10}B and ^{11}B isotopes. Nuclear and electronic degrees of freedom couple through many-body Coulomb interactions.

Contact pairs of RNA with magnesium ions-electrostatics beyond the Poisson-Boltzmann equation.

The electrostatic interaction of RNA with its aqueous environment is most relevant for defining macromolecular structure and biological function. The attractive interaction of phosphate groups in the RNA backbone with ions in the water environment leads to the accumulation of positively charged ions in the first few hydration layers around RNA. Electrostatics of this ion atmosphere and the resulting ion concentration profiles have been described by solutions of the nonlinear Poisson-Boltzmann equation and atomistic molecular dynamics (MD) simulations. Much less is known on contact pairs of RNA phosphate groups with ions at the RNA surface, regarding their abundance, molecular geometry, and role in defining RNA structure. Here, we present a combined theoretical and experimental study of interactions of a short RNA duplex with magnesium (Mg2+) ions. MD simulations covering a microsecond time range give detailed hydration geometries as well as electrostatics and spatial arrangements of phosphate-Mg2+ pairs, including both pairs in direct contact and separated by a single water layer. The theoretical predictions are benchmarked by linear infrared absorption and nonlinear two-dimensional infrared spectra of the asymmetric phosphate stretch vibration which probes both local interaction geometries and electric fields. Contact pairs of phosphate groups and Mg2+ ions are identified via their impact on the vibrational frequency position and line shape. A quantitative analysis of infrared spectra for a range of Mg2+-excess concentrations and comparison with fluorescence titration measurements shows that on average 20-30% of the Mg2+ ions interacting with the RNA duplex form contact pairs. The experimental and MD results are in good agreement. In contrast, calculations based on the nonlinear Poisson-Boltzmann equation fail in describing the ion arrangement, molecular electrostatic potential, and local electric field strengths correctly. Our results underline the importance of local electric field mapping and molecular-level simulations to correctly account for the electrostatics at the RNA-water interface.

Compact OPCPA system seeded by a Cr:ZnS laser for generating tunable femtosecond pulses in the MWIR.

A compact mid-wavelength infrared (MWIR) optical parametric chirped pulse amplification (OPCPA) system generates sub-150 fs pulses at wavelengths from 5.4 to 6.8 µm with >400µJ energy at a 1 kHz repetition rate. A femtosecond Cr:ZnS master oscillator emitting 40 fs pulses at 2.4 µm seeds both a Ho:YLF regenerative amplifier and a two-stage OPCPA based on ZnGeP2 crystals. The 2.05 µm few-picosecond pump pulses from the Ho:YLF amplifier have an energy of 13.4 mJ. Seed pulses for the OPCPA are generated by soliton self-frequency shifting in a fluoride fiber and are tunable between 2.8 and 3.25 µm with a sub-100 fs duration and few-nanojoule energy. The intense MWIR pulses hold strong potential for applications in ultrafast mid-infrared nonlinear optics and spectroscopy.

Compact high-flux hard X-ray source driven by femtosecond mid-infrared pulses at a 1 kHz repetition rate.

A novel, to the best of our knowledge, table-top hard X-ray source driven by femtosecond mid-infrared pulses provides 8 keV pulses at a 1 kHz repetition rate with an unprecedented flux of up to 1.5×1012 X-ray photons/s. Sub-100 fs pulses at a center wavelength of 5 µm and multi-millijoule energy are generated in a four-stage optical parametric chirped-pulse amplifier and focused onto a thin Cu tape target. Electrons are extracted from the target and accelerated in a vacuum up to 100 keV kinetic energy during the optical cycle; the electrons generate a highly stable K α photon flux from the target in a transmission geometry.

Terahertz Polaron Oscillations of Electrons Solvated in Liquid Water.

The terahertz (THz) response of solvated electrons in liquid water is studied in nonlinear ultrafast pump-probe experiments. Free electrons with concentrations from c_{e}=4 to 140×10^{-6} moles/liter are generated by high-field THz or near-infrared multiphoton excitation. The time-resolved change of the dielectric function as mapped by broadband THz pulses exhibits pronounced oscillations persisting up to 30 ps. Their frequency increases with electron concentration from 0.2 to 1.5 THz. The oscillatory response is assigned to impulsively excited coherent polarons involving coupled electron and water shell motions with a frequency set by the local electric field.

Two-dimensional terahertz spectroscopy of condensed-phase molecular systems.

Nonlinear terahertz (THz) spectroscopy relies on the interaction of matter with few-cycle THz pulses of electric field amplitudes up to megavolts/centimeter (MV/cm). In condensed-phase molecular systems, both resonant interactions with elementary excitations at low frequencies such as intra- and intermolecular vibrations and nonresonant field-driven processes are relevant. Two-dimensional THz (2D-THz) spectroscopy is a key method for following nonequilibrium processes and dynamics of excitations to decipher the underlying interactions and molecular couplings. This article addresses the state of the art in 2D-THz spectroscopy by discussing the main concepts and illustrating them with recent results. The latter include the response of vibrational excitations in molecular crystals up to the nonperturbative regime of light-matter interaction and field-driven ionization processes and electron transport in liquid water.

Two-color two-dimensional terahertz spectroscopy: A new approach for exploring even-order nonlinearities in the nonperturbative regime.

Nonlinear two-dimensional terahertz (2D-THz) spectroscopy at frequencies of the emitted THz signal different from the driving frequencies allows for exploring the regime of (off-)resonant even-order nonlinearities in condensed matter. To demonstrate the potential of this method, we study two phenomena in the nonlinear THz response of bulk GaAs: (i) The nonlinear THz response to a pair of femtosecond near-infrared pulses unravels novel fourth- and sixth-order contributions involving interband shift currents, Raman-like excitations of transverse-optical phonon and intervalence-band coherences. (ii) Transient interband tunneling of electrons driven by ultrashort mid-infrared pulses can be effectively controlled by a low-frequency THz field with amplitudes below 50 kV/cm. The THz field controls the electron-hole separation modifying decoherence and the irreversibility of carrier generation.

Spatial distribution of electric-field enhancement across the gap of terahertz bow-tie antennas.

The electric-field enhancement in terahertz (THz) antennas designed for nonlinear THz spectroscopy of soft matter is characterized by spatially resolved electrooptic sampling. To mimic the relevant interaction geometry, metallic, resonant bow-tie antennas are deposited on a thin zinc telluride crystal of 10 µm thickness. The THz electric field transmitted through the antenna gap is recorded by electrooptic sampling. By focusing the 800 nm, sub-20 fs sampling pulses, we achieve a spatial resolution of some 3 µm, which is 1/3 to 1/8 of the antenna-gap width. The THz field in the gap displays an enhancement by a factor of up to 4.5 with a pronounced spectral variation, depending sensitively on the antenna-arm length and the gap width. By scanning the 800 nm probe spot laterally through the antenna gap, the spatial variation of the enhancement is determined, reaching the highest values at the edges of the gap. The results are in agreement with simulations of the electric-field distributions by finite-element calculations.

2.05 µm chirped pulse amplification system at a 1 kHz repetition rate-2.4 ps pulses with 17 GW peak power.

Ho-doped yttrium lithium fluoride chirped pulse amplification (CPA) is implemented with a high-gain regenerative amplifier (RA) and a two-stage booster amplifier. We demonstrate the generation of 52.5 mJ pulses with a duration of 2.4 ps at a 1 kHz repetition rate. A peak power of 17 GW is achieved for the 2050 nm pulses. The CPA displays a remarkably high stability with a pulse-to-pulse rms as low as 0.23%. The RA operates without any signs of bifurcation and delivers 12 mJ pulses. Seeding the booster amplifier with the RA output scales the pulse energy linearly up into the 50-60 mJ range. The amplifier system is operated at room temperature and shows a high optical-to-optical efficiency of 20.3% with respect to the optical pump power.

Multi-millijoule, few-cycle 5 µm OPCPA at 1 kHz repetition rate.

A table-top midwave-infrared optical parametric chirped pulse amplification (OPCPA) system generates few-cycle pulses with multi-10 GW peak power at a 1 kHz repetition rate. The all-optically synchronized system utilizes ZnGeP2 nonlinear crystals and a highly stable 2 µm picosecond pump laser based on Ho:YLiF4. An excellent energy extraction is achieved by reusing the pump pulse after the third parametric power amplification stage, resulting in 3.4 mJ idler pulses at a center wavelength of 4.9 µm. Pulses as short as 89.4 fs are achieved, close to only five optical cycles. Taking into account the pulse energy, a record high peak power of 33 GW for high-energy mid-IR OPCPAs beyond 4 µm wavelength is demonstrated.

Frequency Upshift of the Transverse Optical Phonon Resonance in GaAs by Femtosecond Electron-Hole Excitation.

The impact of transient electric currents on the transverse optical (TO) phonon resonance is studied after excitation by two femtosecond near-infrared pulses via the fourth-order nonlinear terahertz emission. Nonlinear signals due to interband shift currents and heavy-hole-light-hole polarizations are separated from Raman-induced TO phonon coherences. The latter display a frequency upshift by some 100 GHz upon interband excitation of an electron-hole plasma. The frequency shift is caused by transverse electronic shift currents, which modify the dielectric function. A local-field model based on microscopic current densities reproduces the observed frequency upshift.

Self-imaging of tailored vortex pulse arrays and spectral Gouy rotation echoes.

Self-imaging of femtosecond pulses with orbital angular momentum is studied in spectral domain by illuminating the orthogonal arrays of spiral gratings. Spectral Gouy rotation, i.e., the characteristic circulation of extremal regions near phase singularities in spatial spectral maps, is found to partially reappear at discrete distances. The self-imaging of co-rotating and counter-rotating vortices is compared in intensity and spectral behavior. High-selectivity pattern recognition from weakly modulated spectral maps is demonstrated by analyzing spectral moments. By our experiments, the classical Talbot effect is extended to polychromatic pulsed vortex arrays with controlled maps of rotation sign.

Terahertz Driven Amplification of Coherent Optical Phonons in GaAs Coupled to a Metasurface.

We demonstrate amplification of longitudinal optical (LO) phonons by polar-optical interaction with an electron plasma in a GaAs structure coupled to a metallic metasurface using two-color two-dimensional spectroscopy. In a novel scheme, the metamaterial resonator enhances broadband terahertz fields, which generate coherent LO phonons and drive free electrons in the conduction band of GaAs. The time evolution of the LO phonon amplitude is monitored with midinfrared pulses via the LO-phonon-induced Kerr nonlinearity of the sample, showing an amplification of the LO phonon amplitude by up to a factor of 10, in agreement with a theoretical estimate.

Water Dynamics in the Hydration Shells of Biomolecules.

The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water.

Recent advances in ultrafast X-ray sources.

Over more than a century, X-rays have transformed our understanding of the fundamental structure of matter and have been an indispensable tool for chemistry, physics, biology, materials science and related fields. Recent advances in ultrafast X-ray sources operating in the femtosecond to attosecond regimes have opened an important new frontier in X-ray science. These advances now enable: (i) sensitive probing of structural dynamics in matter on the fundamental timescales of atomic motion, (ii) element-specific probing of electronic structure and charge dynamics on fundamental timescales of electronic motion, and (iii) powerful new approaches for unravelling the coupling between electronic and atomic structural dynamics that underpin the properties and function of matter. Most notable is the recent realization of X-ray free-electron lasers (XFELs) with numerous new XFEL facilities in operation or under development worldwide. Advances in XFELs are complemented by advances in synchrotron-based and table-top laser-plasma X-ray sources now operating in the femtosecond regime, and laser-based high-order harmonic XUV sources operating in the attosecond regime. This article is part of the theme issue 'Measurement of ultrafast electronic and structural dynamics with X-rays'.