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Thomas Elsaesser

Publications and source records attributed to Thomas Elsaesser.

17 recordsLinked to original sources
arXiv2025

Solvated electrons in polar liquids as epsilon-near-zero materials tunable in the terahertz frequency range

Electrons in polar liquids give rise to a polaron resonance at a terahertz (THz) frequency \nu_0 depending on electron concentration. The impact of this resonance on light propagation is studied in experiments, where a femtosecond pump pulse generates electrons via multiphoton ionization and a THz probe pulse propagated through the excited sample is detected in a phase-resolved way. We observe a behavior characteristic for epsilon-near-zero (ENZ) materials with strongly modified phase and group velocities around \nu_0, and a broadening of the THz pulse envelope below \nu_0. Calculations based on a local-field approach reproduce the ENZ behavior.

physics.chem-ph↗
arXiv2024

Tuning the terahertz response of liquids by creating polar many-body excitations

A surprising result from the theory of quantum control is the degree to which the properties of a physical system can be manipulated. Both atomic and many-body solid state models admit the possibility of creating a 'driven imposter', in which the optical response of one material mimics that of a dynamically distinct system. Here we apply these techniques to polarons in polar liquids. Such quasiparticles describe solvated electrons interacting with many-body degrees of freedom of their environment. The polaron frequency, which depends on the electron concentration in the liquid, is controlled with a pump field, rendering the polaron frequency of three different liquids identical. The experiments demonstrate the feasibility of 'polar impostorons', a so far purely theoretical phenomenon.

quant-ph↗
arXiv2023

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$_e \approx$ 800 $μ$M 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 THz 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.

physics.chem-ph↗
arXiv2022

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 in the role of fluctuating electric fields of the liquid for generating electrons in presence of an external terahertz field and address polaronic many-body properties of solvated electrons. The article combines a review of recent results from experiment and theory with a discussion of basic electric interactions of electrons in water.

physics.chem-ph↗
arXiv2021

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 frequency 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.

physics.chem-ph↗
arXiv2021

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.

physics.chem-ph↗
arXiv2021

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.

physics.chem-ph↗
arXiv2021

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 \times 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.

physics.chem-ph↗
arXiv2020

Field-Induced Tunneling Ionization and Terahertz-Driven Electron Dynamics in Liquid Water

Liquid water at ambient temperature displays ultrafast molecular motions and concomitant fluctuations of very strong electric fields originating from the dipolar H2O molecules. We show that such random intermolecular fields induce tunnel ionization of water molecules, which becomes irreversible if an external terahertz (THz) pulse imposes an additional directed electric field on the liquid. Time-resolved nonlinear THz spectroscopy maps charge separation, transport and localization of the released electrons on a few-picosecond time scale. The highly polarizable localized electrons modify the THz absorption spectrum and refractive index of water, a manifestation of a highly nonlinear response. Our results demonstrate how the interplay of local electric field fluctuations and external electric fields allows for steering charge dynamics and dielectric properties in aqueous systems.

physics.chem-ph↗
arXiv2020

Aqueous Contact Ion Pairs of Phosphate Groups with Na$^+$, Ca$^{2+}$ and Mg$^{2+}$ -- Structural Discrimination by Femtosecond Infrared Spectroscopy and Molecular Dynamics Simulations

The extent of contact and solvent shared ion pairs of phosphate groups with Na$^+$, Ca$^{2+}$ and Mg$^{2+}$ ions in aqueous environment and their relevance for the stability of polyanionic DNA and RNA structures is highly debated. Employing the asymmetric phosphate stretching vibration of dimethyl phosphate (DMP), a model system of the sugar-phosphate backbone of DNA and RNA, we present linear infrared, femtosecond infrared pump-probe and absorptive 2D-IR spectra that report on contact ion pair formation via the presence of blue shifted spectral signatures. Compared to the linear infrared spectra, the nonlinear spectra reveal contact ion pairs with increased sensitivity because the spectra accentuate differences in peak frequency, transition dipole moment strength, and excited state lifetime. The experimental results are corroborated by long time scale MD simulations, benchmarked by density functional simulations on phosphate-ion-water clusters. The microscopic interpretation reveals subtle structural differences of ion pairs formed by the phosphate group and the ions Na$^+$, Ca$^{2+}$ and Mg$^{2+}$. Intricate properties of the solvation shell around the phosphate group and the ion are essential to explain the experimental observations. The present work addresses a challenging to probe topic with the help of a model system and establishes new experimental data of contact ion pair formation, thereby underlining the potential of nonlinear 2D-IR spectroscopy as an analytical probe of phosphate-ion interactions in complex biological systems.

physics.chem-ph↗
arXiv2020

Change of Hydration Patterns upon RNA Melting Probed by Excitations of Phosphate Backbone Vibrations

The water hydration shell has decisive impact on the structural and functional properties of RNA. Changes of RNA structure upon melting and in biochemical processes are accompanied by a change of hydration patterns, a process which is barely characterized. To discern hydration geometries around the backbone phosphate groups of an RNA double helix at the molecular level, we combine two-dimensional infrared spectroscopy of phosphate vibrations with theoretical simulations. There are three distinct coexisting hydration motifs of the RNA A-helix, an ordered chain-like arrangement of water molecules with links between neighboring phosphate groups, separate local hydration shells of up to six water molecules, and hydrated phosphate/counterion contact pairs. RNA disordering upon melting is connected with a transition from predominant ordered water structures to local hydration shells around phosphate units. Structural fluctuations are dominated by librational water motions occurring on a 300 fs time scale, without exchange between hydration motifs.

physics.chem-ph↗
arXiv2019

Contact Ion Pairs of Phosphate Groups in Water -- Two-Dimensional Infrared Spectroscopy of Dimethyl-Phosphate and Ab-Initio Simulations

The interaction of phosphate groups with ions in an aqueous environment has a strong impact on the structure and folding processes of DNA and RNA. The dynamic variety of ionic arrangements, including both contact pairs and water separated ions, and the molecular coupling mechanisms are far from being understood. In a combined experimental and theoretical approach, we address the properties of contact ion pairs of the prototypical system dimethyl-phosphate with Na$^+$, Ca$^{2+}$, and Mg$^{2+}$ ions in water. Linear and femtosecond two-dimensional infrared (2D-IR) spectroscopy of the asymmetric (PO$_2$)$^-$ stretching vibration separates and characterizes the different species via their blue-shifted vibrational signatures and 2D-IR lineshapes. Phosphate-magnesium contact pairs stand out as the most compact geometry while the contact pairs with Ca$^{2+}$ and Na$^+$ display a wider structural variation. Microscopic density functional theory simulations rationalize the observed frequency shifts and reveal distinct differences between the contact geometries.

physics.chem-ph↗
arXiv2019

Noncovalent Interactions of Hydrated DNA and RNA Mapped by 2D-IR Spectroscopy

Biomolecules couple to their aqueous environment through a variety of noncovalent interactions. Local structures at the surface of DNA and RNA are frequently determined by hydrogen bonds with water molecules, complemented by non-specific electrostatic and many-body interactions. Structural fluctuations of the water shell result in fluctuating Coulomb forces on polar and/or ionic groups of the biomolecular structure and in a breaking and reformation of hydrogen bonds. Two-dimensional infrared (2D-IR) spectroscopy of vibrational modes of DNA and RNA gives insight into local hydration geometries, elementary molecular dynamics, and the mechanisms behind them. In this chapter, recent results from 2D-IR spectroscopy of native and artificial DNA and RNA are presented, together with theoretical calculations of molecular couplings and molecular dynamics simulations. Backbone vibrations of DNA and RNA are established as sensitive noninvasive probes of the complex behavior of hydrated helices. The results reveal the femtosecond fluctuation dynamics of the water shell, the short-range character of Coulomb interactions, and the strength and fluctuation amplitudes of interfacial electric fields.

physics.chem-ph↗
arXiv2019

Hydrated Excess Protons in Acetonitrile/Water Mixtures - Solvation Species and Ultrafast Proton Motions

The solvation structure of protons in aqueous media is highly relevant to electric properties and to proton transport in liquids and membranes. At ambient temperature, polar liquids display structural fluctuations on femto- to picosecond time scales with a direct impact on proton solvation. We apply two-dimensional infrared (2D-IR) spectroscopy for following proton dynamics in acetonitrile/water mixtures with the Zundel cation H$_5$O$_2^+$ prepared in neat acetonitrile as a benchmark. The 2D-IR spectra of the proton transfer mode of H$_5$O$_2^+$ demonstrate stochastic large-amplitude motions in the double-minimum proton potential, driven by fluctuating electric fields. In all cases the excess proton is embedded in a water dimer, forming an H$_5$O$_2^+$ complex as major solvation species. This observation is rationalized by quantum mechanics/molecular mechanics molecular dynamics simulations including up to 4 water molecules embedded in acetonitrile. The Zundel motif interacts with its closest water neighbor in an H$_7$O$_3^+$ unit without persistent proton localization.

physics.chem-ph↗
arXiv2015

Nanoscale Transport of Surface Excitons at the Interface between ZnO and a Molecular Monolayer

Excitons play a key role for the optoelectronic properties of hybrid systems. We apply near-field scanning optical microscopy (NSOM) with a $100\,\text{-nm}$ spatial resolution to study the photoluminescence of surface excitons (SX) in a $20\,\text{nm}$ thick ZnO film capped with a monolayer of stearic acid molecules. Emission from SX, donor-bound (DX), and - at sample temperatures $T>20\,\text{K}$ - free (FX) excitons is separated in steady-state and time-resolved photoluminescence spectra. The $4\,\text{meV}$ broad smooth envelope of SX emission at $T<10\,\text{K}$ points to an inhomogeneous distribution of SX transition energies and spectral diffusion caused by diffusive SX transport on a $50\,\text{nm}$ scale with a SX diffusion coefficient of $D(T<10 K)=0.30\,\text{cm$^2$/s}$.

cond-mat.mes-hall↗