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.

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.

Transient Terahertz Stark Effect: A Dynamic Probe of Electric Interactions in Polar Liquids.

Electric forces acting on molecules in liquids at ambient temperature fluctuate at terahertz (THz) frequencies with a direct impact on their electronic and optical properties. We introduce the transient THz Stark effect to modify the electronic absorption spectra of dye molecules and, thus, elucidate and determine the underlying molecular interactions and dynamics. Picosecond electric fields of megavolts/cm induce a nonequilibrium response of the prototypical Betaine-30 in polar solution that is probed via transient absorption changes. The field-induced broadening of the absorption band follows the THz intensity in time, with a minor impact of solvent dynamics. The ground and excited state dipole energies in the THz field govern this response, allowing for a quantification of electric forces in a structurally frozen molecular environment.

Short-Range Cooperative Slow-down of Water Solvation Dynamics Around SO4 2--Mg2+ Ion Pairs.

The presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg2+ and SO4 2- ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO4 2- stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO4 2- ions around 1100 cm-1 reveals a specific slow-down of solvation dynamics for hydrated MgSO4 and for Na2SO4 in the presence of Mg2+ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na2SO4 solutions in the absence of Mg2+ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO4 2--Mg2+ ion pairs.

Ultrafast Vibrational Response of Activated C-D Bonds in a Chloroform-Platinum(II) Complex.

The vibrational response of the activated C-D bond in the chloroform complex [Pt(C6H5)2(btz-N,N')·CDCl3, where btz = 2,2'-bi-5,6-dihydro-4H-1,3-thiazine] is studied by linear and nonlinear two-dimensional infrared (2D-IR) spectroscopy. The change of the C-D stretching vibration of metal-coordinated CDCl3 relative to the free solvent molecule serves as a measure of the non-classical Pt···D-C interaction strength. The stretching absorption band of the activated C-D bond displays a red shift of 119 cm-1 relative to uncoordinated CDCl3, a strong broadening, and an 8-fold enhancement of spectrally integrated absorption. The infrared (IR) absorption and 2D-IR line shapes are governed by spectral diffusion on 200 fs and 2 ps time scales, induced by the fluctuating solvent CDCl3. The enhanced vibrational absorption and coupling to solvent forces are assigned to the enhanced electric polarizability of the activated C-D bond. Density functional theory calculations show a significant increase of C-D bond polarizability of CDCl3 upon coordination to the 16 valence electron Pt(II) complex.

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.

Field-Induced Electron Generation in Water: Solvation Dynamics and Many-Body Interactions.

The solvated electron represents an elementary quantum system in a liquid environment. Electrons solvated in water have raised strong interest because of their prototypical properties, their role in radiation chemistry, and their relevance for charge separation and transport. Nonequilibrium dynamics of photogenerated electrons in water occur on ultrafast time scales and include charge transfer, localization, and energy dissipation processes. We present new insight into the role of fluctuating electric fields of the liquid for generating electrons in the presence of an external terahertz field and address polaronic many-body properties of solvated electrons. This Perspective combines a review of recent results from experiment and theory with a discussion of basic electric interactions of electrons in water.

Underdamped longitudinal soft modes in ionic crystallites-lattice and charge motions observed by ultrafast x-ray diffraction.

Soft modes in crystals are lattice vibrations with frequencies that decrease and eventually vanish as the temperature approaches a critical point, e.g., a structural change due to a phase transition. In ionic para- or ferroelectric materials, the frequency decrease is connected with a diverging electric susceptibility and, for infrared active modes, a strong increase in oscillator strength. The traditional picture describes soft modes as overdamped transverse optical phonons of a hybrid vibrational-electronic character. In this context, potassium dihydrogen phosphate (KH2PO4, KDP) has been studied for decades as a prototypical material with, however, inconclusive results regarding the soft modes in its para- and ferroelectric phase. There are conflicting assignments of soft-mode frequencies and damping parameters. We report the first observation of a longitudinal underdamped soft mode in paraelectric KDP. Upon impulsive femtosecond Raman excitation of coherent low-frequency phonons in the electronic ground state of KDP crystallites, transient powder diffraction patterns are recorded with femtosecond hard x-ray pulses. Electron density maps derived from the x-ray data reveal oscillatory charge relocations over interatomic distances, much larger than the sub-picometer nuclear displacements, a direct hallmark of soft-mode behavior. The strongly underdamped character of the soft mode manifests in charge oscillations persisting for more than 10 ps. The soft-mode frequency decreases from 0.55 THz at T = 295 K to 0.39 THz at T = 175 K. An analysis of the Raman excitation conditions in crystallites and the weak damping demonstrate a longitudinal character. Our results extend soft-mode physics well beyond the traditional picture and pave the way for an atomic-level characterization of soft modes.

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.

Coherent polaron dynamics of electrons solvated in polar liquids.

An electron solvated in a polar liquid is an elementary quantum system with properties governed by electric interactions with a fluctuating molecular environment. In the prevailing single particle picture, the quantum ground and excited states are determined by a self-consistent potential, as defined by the particular local configuration of the solvation shell. This description neglects collective many-body excitations, which arise from the coupling of electronic degrees of freedom and nuclear motions of the environment. While recent experiments have demonstrated collective nonequilbrium electronic-nuclear motion, i.e. polaron excitations in liquid water, their relevance in the broader context of polar liquids has remained unexplored. Here, we study the nonequilibrium dielectric response of the, compared to water, less polar alcohols isopropanol, and ethylene glycol, that also display a different hydrogen bond pattern. We demonstrate that ultrafast relaxation of photogenerated electrons impulsively induces coherent charge oscillations, which persist for some 10 ps. They emit electric waves in a frequency range from 0.1 to 2 THz, depending on electron concentration. Oscillation frequencies and line shapes are reproduced by a unified polaron picture for alcohols and water, which is based on a Clausius-Mossotti local field approach for the THz dielectric function. The analysis suggests a longitudinal character of many-body polaron excitations and a weak coupling to transverse excitations, supported by the underdamped character of charge oscillations. Polaron dynamics are governed by the long-range Coulomb interaction between an excess electron and several thousands of polar solvent molecules, while local electron solvation geometries play a minor role.

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.

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.

Phosphate Vibrations Probe Electric Fields in Hydrated Biomolecules: Spectroscopy, Dynamics, and Interactions.

Electric interactions have a strong impact on the structure and dynamics of biomolecules in their native water environment. Given the variety of water arrangements in hydration shells and the femto- to subnanosecond time range of structural fluctuations, there is a strong quest for sensitive noninvasive probes of local electric fields. The stretching vibrations of phosphate groups, in particular the asymmetric (PO2)- stretching vibration νAS(PO2)-, allow for a quantitative mapping of dynamic electric fields in aqueous environments via a field-induced redshift of their transition frequencies and concomitant changes of vibrational line shapes. We present a systematic study of νAS(PO2)- excitations in molecular systems of increasing complexity, including dimethyl phosphate (DMP), short DNA and RNA duplex structures, and transfer RNA (tRNA) in water. A combination of linear infrared absorption, two-dimensional infrared (2D-IR) spectroscopy, and molecular dynamics (MD) simulations gives quantitative insight in electric-field tuning rates of vibrational frequencies, electric field and fluctuation amplitudes, and molecular interaction geometries. Beyond neat water environments, the formation of contact ion pairs of phosphate groups with Mg2+ ions is demonstrated via frequency upshifts of the νAS(PO2)- vibration, resulting in a distinct vibrational band. The frequency positions of contact geometries are determined by an interplay of attractive electric and repulsive exchange interactions.

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.

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.

Magnesium Contact Ions Stabilize the Tertiary Structure of Transfer RNA: Electrostatics Mapped by Two-Dimensional Infrared Spectra and Theoretical Simulations.

Ions interacting with hydrated RNA play a central role in defining its secondary and tertiary structure. While spatial arrangements of ions, water molecules, and phosphate groups have been inferred from X-ray studies, the role of electrostatic and other noncovalent interactions in stabilizing compact folded RNA structures is not fully understood at the molecular level. Here, we demonstrate that contact ion pairs of magnesium (Mg2+) and phosphate groups embedded in local water shells stabilize the tertiary equilibrium structure of transfer RNA (tRNA). Employing dialyzed tRNAPhe from yeast and tRNA from Escherichia coli, we follow the population of Mg2+ sites close to phosphate groups of the ribose-phosphodiester backbone step by step, combining linear and nonlinear infrared spectroscopy of phosphate vibrations with molecular dynamics simulations and ab initio vibrational frequency calculations. The formation of up to six Mg2+/phosphate contact pairs per tRNA and local field-induced reorientations of water molecules balance the phosphate-phosphate repulsion in nonhelical parts of tRNA, thus stabilizing the folded structure electrostatically. Such geometries display limited sub-picosecond fluctuations in the arrangement of water molecules and ion residence times longer than 1 µs. At higher Mg2+ excess, the number of contact ion pairs per tRNA saturates around 6 and weakly interacting ions prevail. Our results suggest a predominance of contact ion pairs over long-range coupling of the ion atmosphere and the biomolecule in defining and stabilizing the tertiary structure of tRNA.