arXiv subjects

Martina Havenith

Publications and source records attributed to Martina Havenith.

8 recordsLinked to original sources

arXiv2025

Light-induced quantum friction of carbon nanotubes in water

Quantum friction describes the transfer of energy and momentum from electronically excited states in a material to a surrounding solvent. Here, we show that near-infrared (NIR) fluorescent single-walled carbon nanotubes (SWCNTs) exhibit quantum friction in water. The diffusion constants of functionalized SWCNTs in aqueous solution decrease linearly by around 50 % with increasing excitation power. In contrast, SWCNTs with quantum defects that localize excitons show no power-dependent diffusion. Chemical manipulation of exciton concentration by molecules that increase or decrease SWCNT fluorescence also modulate the diffusion constant by a factor of up to 2. Additionally, excitons increase the macroscopic viscosity of SWCNT solutions. Optical pump Terahertz (THz) probe spectroscopy reveals transient absorption features of water (37 /cm and above 80 /cm), indicating energy dissipation into translational modes of its hydrogen bond network. Molecular dynamics simulations further support a mechanism in which exciton-induced dipoles enhance frictional forces. These findings establish that excitons in SWCNTs induce quantum friction in water.

physics.optics↗

arXiv2024

High-Dynamic Range Broadband Terahertz Time-Domain Spectrometer Based on Organic Crystal MNA

We present a high power and broadband THz-TDS setup utilizing the nonlinear organic crystal MNA both as emitter and detector. The THz source is based on optical rectification of near infra-red laser pulses at a central wavelength of 1036 nm from a commercial, high-power Yb-based laser system and reaches a high THz average power of 11 mW at a repetition rate of 100 kHz and a broad and smooth bandwidth of more than 9 THz. The conversion efficiency is high (0.13%) in spite of the high excitation average power of 8 W. We validate the high dynamic range and reliability of the source for applications in linear spectroscopy by measuring the broadband THz properties of chi(2) nonlinear crystals up to 8 THz. This new high-repetition rate source is very promising for ultra-broadband THz spectroscopy at high dynamic range and/or reduced measurement times.

physics.optics↗

arXiv2022

Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions

Signatures of solvated excess protons in infrared difference absorption spectra, such as the continuum band between the water bend and stretch bands, have been experimentally known for a long time, but the theoretical basis for linking spectral signatures with the microscopic proton-transfer mechanism so far relied on normal-mode analysis. We analyze the excess-proton dynamics in ab initio molecular-dynamics simulations of aqueous hydrochloric acid solutions by trajectory-decomposition techniques. The continuum band in the 2000 - 3000 cm$^{-1 }$ range is shown to be due to normal-mode oscillations of temporary H$_3$O$^+$ complexes. An additional prominent peak at 400 cm$^{-1}$ reports on the coupling of excess-proton motion to the relative vibrations of the two flanking water molecules. The actual proton transfer between two water molecules, which for large water separations involves crossing of a barrier and thus is not a normal mode, is characterized by two characteristic time scales: Firstly, the waiting time for transfer to occur in the range of 200 - 300 fs, which leads to a broad weak shoulder around ~100 cm$^{-1}$, consistent with our experimental THz spectra. Secondly, the mean duration of a transfer event of about 14 fs, which produces a rather well-defined spectral contribution around 1200 cm$^{-1}$ and agrees in location and width with previous experimental mid-infrared spectra.

physics.chem-ph↗

arXiv2021

Water Solvation of Charged and Neutral Gold Nanoparticles

Gold nanoparticles are unique electrocatalysts for oxygen reduction, carbon dioxide reduction, and alcohol oxidation. Electrocatalytic processes are influenced by the interaction with the solvent, yet the direct investigation of the solvation of nanoparticles is scarce. Here we select gold nanoparticles as 10 nm sized solutes of which we can control the charge. We perform mid-infrared and terahertz spectroscopy to compare the behavior of the water in solution with micelles loaded with neutral and positive gold nanoparticles. We find indications that the hydration water around the gold-loaded micelles is characterized by weaker hydrogen bonds than bulk water. A positive nanoparticle charge is observed to result in a larger blue shift of the OH stretch, quenches the intensity of the collective translational mode, and increases the absorption by librating water molecules. Water at the interface of a positive gold nanoparticle could experience a stiffer potential energy surface which, in turn, might unveil local thermodynamic properties.

physics.chem-ph↗

arXiv2020

Size-dependence of hydrophobic hydration at electrified gold/water interfaces

Hydrophobic hydration at metal/water interfaces actively contributes to the energetics of electrochemical reactions, e.g. CO$_2$ and N$_2$ reduction, where small hydrophobic molecules are involved. In this work, constant applied potential molecular dynamics is employed to study hydrophobic hydration at a gold/water interface. We propose an extension of the Lum-Chandler-Weeks (LCW) theory to describe the free energy of hydrophobic hydration at the interface as a function of solute size and applied voltage. Based on this model we are able to predict the free energy cost of cavity formation at the interface directly from the free energy cost in the bulk plus an interface-dependent correction term. The interfacial water network contributes significantly to the free energy yielding a preference for outer-sphere adsorption at the gold surface for ideal hydrophobes. We predict an accumulation of small hydrophobic solutes of sizes comparable to CO or N$_2$, while the free energy cost to hydrate larger hydrophobes, above 2.5 Angstrom radius, is shown to be greater at the interface than in the bulk. Interestingly, the transition from the volume dominated to the surface dominated regimes predicted by the LCW theory in the bulk is also found to take place for hydrophobes at the Au/water interface, but occurs at smaller cavity radii. By applying the extended LCW theory to a simple model addition reaction, we illustrate some implications of our findings for electrochemical reactions.

physics.chem-ph↗

arXiv2020

An Isolated Water Droplet in the Aqueous Solution of a Supramolecular Tetrahedral Cage

Water under nanoconfinement at ambient conditions has exhibited low-dimensional ice formation and liquid-solid phase transitions, but with structural and dynamical signatures which map onto known regions of waters phase diagram. Using THz absorption spectroscopy and ab initio molecular dynamics, we have investigated the ambient water confined in a supramolecular tetrahedral assembly, and determined that a distinct network of 9-10 water molecules is present within the nanocavity of the host. The low-frequency absorption spectrum and theoretical analysis of the water in the $Ga_4$$L_6$$^{-12}$ host demonstrate that the structure and dynamics of the encapsulated droplet is distinct from any known phase of water. A further inference is that the release of the highly unusual encapsulated water droplet creates a strong thermodynamic driver for the high affinity binding of guests in aqueous solution for the $Ga_4$$L_6$$^{-12}$ supramolecular construct.

physics.chem-ph↗

arXiv2020

Strong Anisotropy in Liquid Water upon Librational Excitation using Terahertz Laser Fields

Tracking the excitation of water molecules in the homogeneous liquid is challenging due to the ultrafast dissipation of rotational excitation energy through the hydrogen-bonded network. Here we demonstrate strong transient anisotropy of liquid water through librational excitation using single-color pump-probe experiments at 12.3 THz. We deduce a third order response of chi^3 exceeding previously reported values in the optical range by three orders of magnitude. Using a theory that replaces the nonlinear response with a material response property amenable to molecular dynamics simulation, we show that the rotationally damped motion of water molecules in the librational band is resonantly driven at this frequency, which could explain the enhancement of the anisotropy in the liquid by the external Terahertz field. By addition of salt (MgSO4), the hydration water is instead dominated by the local electric field of the ions, resulting in reduction of water molecules that can be dynamically perturbed by THz pulses.

physics.chem-ph↗

arXiv2016

Design of a plasmonic near-field tip for super-resolution IR-imaging

The concepts of spoof surface plasmon polaritons and adiabatic field compression are employed to design metallic near-field probes that allow guiding and focusing of mid-infrared wavelength electromagnetic radiation and provides subwavelength field confinements and a lateral optical resolution of about 10 nm.

physics.optics↗