arXiv subjects

Martin Richter

Publications and source records attributed to Martin Richter.

At least 19 recordsLinked to original sources

arXiv2023

On Direction Preserving Discretizations for Computing Phase-Space Densities

Ray flow methods provide efficient tools for modelling wave energy transport in complex systems at high-frequencies. We compare two Petrov-Galerkin discretizations of a phase-space boundary integral model for stationary wave energy densities in two-dimensional domains. The directional dependence is approximated using a finite set of directions oriented into the domain from the boundary. The propagation direction can be preserved across multi-component domains when the directions within the local set for a given region of the boundary are taken as a subset of a global direction set. In this work we compare the use of piecewise constant and piecewise linear test functions, which physically corresponds to the interpolation scheme used when the transport is in a direction not belonging to the finite global set.

physics.comp-ph↗

arXiv2022

A full quantum mechanical approach assessing the chemical and electromagnetic effect in TERS

Tip-enhanced Raman spectroscopy (TERS) is a valuable method for surface analysis with nanometer to angstrom-scale resolution, however, the accurate simulation of particular TERS signals remains a computational challenge. We present a unique approach to this challenge by combining the two main contributors to plasmon-enhanced Raman spectroscopy and to the high resolution in TERS in particular, the electromagnetic and the chemical effect, into one quantum mechanical simulation. The electromagnetic effect describes the sample's interaction with the strong, highly localized and inhomogeneous electric fields associated with the plasmonic tip, and is typically the thematic focus for most mechanistic studies. On the other hand, the chemical effect covers the different responses to the extremely close-range and highly position-sensitive chemical interaction between the apex tip atom(s) and the sample, and, as we could show in previous works, plays an often underestimated role. Starting from a (time-dependent) density functional theory description of the chemical model system, comprised of a tin(II) phthalocyanine (SnPc) sample molecule and a single silver atom as tip, we introduce the electromagnetic effect through a series of point charges that recreate the electric field in the vicinity of the plasmonic Ag nanoparticle. By scanning the tip over the molecule along a 3D grid, we can investigate the system's Raman response on each position for non-resonant and resonant illumination. Simulating both effects on their own already hints at the achievable signal enhancement and resolution, but the combination of both creates even stronger evidence that TERS is capable of resolving sub-molecular features.

physics.chem-ph↗

arXiv2022

Integration of Reconfigurable Intelligent Surfaces in Dynamical Energy Analysis

Reconfigurable intelligent surfaces have been recently investigated for their potentials to offer significant performance improvements in the next generation wireless telecommunication systems (5G and beyond / 6G). Intelligent surfaces are programmed to control the electromagnetic propagation and obtain the desired wavefront by tuning the local reflection phase of unit elements. Predicting the electromagnetic propagation in the RIS-assisted wireless channel accurately is a significant challenge for researchers and becomes crucial for Telecom operators to properly allocate the radio resources. We propose the use of an Eulerian ray-tracing method, the Dynamical Energy Analysis (DEA), as a coverage planning tool capable of account for the EM interaction between reconfigurable intelligent surfaces and the surrounding environment. The main characteristics that make DEA suitable for this purpose are discussed and some preliminary results of the reflective surface integration within the DEA code will be presented.

physics.app-ph↗

arXiv2022

Electromagnetic Illusion in Smart Environments

Metasurfaces can be designed to achieve prescribed functionality. Careful meta-atom design and arrangement achieve homogeneous and inhomogeneous layouts that can enable exceptional capabilities to manipulate incident waves. Inherently, the control of scattering waves is crucial in wireless communications and stealth technologies. Low-profile and light-weight coatings that offer comprehensive manipulation are highly desirable for applications including camouflaging, deceptive sensing, radar cognition control, and defense security. Here, we propose a method that achieves electromagnetic illusion without altering the object. A proof of principle is proposed and practiced for one-dimensional media. The idea is to engineer the environment instead of the object coating. This work paves the way for versatile designs that will improve electromagnetic security applications with the aid of smart environments.

physics.app-ph↗

arXiv2022

Nonadiabatic ab initio molecular dynamics including spin-orbit coupling and laser fields

Nonadiabatic ab initio molecular dynamics (MD) including spin-orbit coupling (SOC) and laser fields is investigated as a general tool for studies of excited-state processes. Up to now, SOCs are not included in standard ab initio MD packages. Therefore, transitions to triplet states cannot be treated in a straightforward way. Nevertheless, triplet states play an important role in a large variety of systems and can now be treated within the given framework. The laser interaction is treated on a non-perturbative level that allows nonlinear effects like strong Stark shifts to be considered. As MD allows for the handling of many atoms, the interplay between triplet and singlet states of large molecular systems will be accessible. In order to test the method, IBr is taken as a model system, where SOC plays a crucial role for the shape of the potential curves and thus the dynamics. Moreover, the influence of the nonresonant dynamic Stark effect is considered. The latter is capable of controlling reaction barriers by electric fields in timereversible conditions, and thus a control laser using this effect acts like a photonic catalyst. In the IBr molecule, the branching ratio at an avoided crossing, which arises from SOC, can be influenced.

physics.chem-ph↗

arXiv2021

A direction preserving discretization for computing phase-space densities

Ray flow methods are an efficient tool to estimate vibro-acoustic or electromagnetic energy transport in complex domains at high-frequencies. Here, a Petrov-Galerkin discretization of a phase-space boundary integral equation for transporting wave energy densities on two-dimensional surfaces is proposed. The directional dependence of the energy density is approximated at each point on the boundary in terms of a finite local set of directions propagating into the domain. The direction of propagation can be preserved for transport across multi-component domains when the directions within the local set are inherited from a global direction set. The range of applicability and computational cost of the method will be explored through a series of numerical experiments, including wave problems from both acoustics and elasticity in both single and multi-component domains. The domain geometries considered range from both regular and irregular polygons to curved surfaces, including a cast aluminium shock tower from a Range Rover car.

math.NA↗

arXiv2021

The chemical effect goes resonant -- a full quantum mechanical approach on TERS

Lately, experimental evidence of unexpectedly extremely high spatial resolution of tip-enhanced Raman scattering (TERS) has been demonstrated. Theoretically, two different contributions are discussed: an electromagnetic effect, leading to a spatially confined near field due to plasmonic excitations; and the so-called chemical effect originating from the locally modified electronic structure of the molecule due to the close proximity of the plasmonic system. Most of the theoretical efforts have concentrated on the electromagnetic contribution or the chemical effect in case of non-resonant excitation. In this work, we present a fully quantum mechanical description including non-resonant and resonant chemical contributions as well as charge-transfer phenomena of these molecular-plasmonic hybrid system at the density functional and the time-dependent density functional level of theory. We consider a surface-immobilized tin(II) phthalocyanine molecule as the molecular system, which is minutely scanned by a plasmonic tip, modeled by a single silver atom. These different relative positions of the Ag atom to the molecule lead to pronounced alterations of the Raman spectra. These Raman spectra vary substantially, both in peak positions and several orders of magnitude in the intensity patterns under non-resonant and resonant conditions, and also, depending on, which electronic states are addressed. Our computational approach reveals that unique - non-resonant and resonant - chemical interactions among the tip and the molecule significantly alter the TERS spectra and are mainly responsible for the high, possibly sub-Angstrom spatial resolution.

physics.chem-ph↗

arXiv2021

A singlet and triplet excited-state dynamics study of the keto and enol tautomers of cytosine

The photoinduced excited-state dynamics of the keto and enol forms of cytosine is investigated using ab initio surface hopping in order to understand the outcome of molecular beam femtosecond pump-probe photoionization spectroscopy experiments. Both singlet and triplet states are included in the dynamics. The results show that triplet states play a significant role in the relaxation of the keto tautomer, while they are less important in the enol tautomer. In both forms, the T$_1$ state minimum is found too low in energy to be detected in standard photoionization spectroscopy experiments and therefore experimental decay times should arise from a simultaneous relaxation to the ground state and additional intersystem crossing followed by internal conversion to the T$_1$ state. In agreement with available experimental lifetimes, we observe three decay constants of 7 fs, 270 fs and 1900 fs - the first two coming from the keto tautomer and the longer one from the enol tautomer. Deactivation of the enol form is due to internal conversion to the ground state via two S$_1$/S$_0$ conical intersections of ethylenic type.

physics.chem-ph↗

arXiv2021

Femtosecond Intersystem Crossing in the DNA Nucleobase Cytosine

Ab initio molecular dynamics including non-adiabatic and spin-orbit couplings on equal footing is used to unravel the deactivation of cytosine after UV light absorption. Intersystem crossing (ISC) is found to compete directly with internal conversion in tens of femtoseconds, thus making cytosine the organic compound with the fastest triplet population calculated so far. It is found that close degeneracy between singlet and triplet states can more than compensate for very small spin-orbit couplings, leading to efficient ISC. The femtosecond nature of the intersystem crossing process highlights its importance in photochemistry and challenges the conventional view that large singlet-triplet couplings are required for an efficient population flow into triplet states. These findings are important to understand DNA photostability and the photochemistry and dynamics of organic molecules in general.

physics.chem-ph↗

arXiv2021

Spatially Resolving the Enhancement Effect in Surface-Enhanced Coherent Anti-Stokes Raman Scattering by Plasmonic Doppler Gratings

In this work, we introduce the platform of plasmonic Doppler grating (PDG) to experimentally investigate the enhancement effect of plasmonic gratings in the input and output beams of nonlinear surface-enhanced coherent anti-Stokes Raman scattering (SECARS). PDGs are designable azimuthally chirped gratings that provide broadband and spatially dispersed plasmonic enhancement. Therefore, they offer the opportunity to observe and compare the overall enhancement from different combinations of enhancement in individual input and output beams. We first confirm PDG's capability of spatially separating the input and output enhancement in linear surface-enhanced fluorescence and Raman scattering. We then investigate spatially resolved enhancement in nonlinear SECARS, where coherent interaction of the pump, Stokes, and anti-Stokes beams is enhanced by the plasmonic gratings. By mapping the SECARS signal and analyzing the azimuthal angle-dependent intensity, we characterize the enhancement at individual frequencies. Together with theoretical analysis, we show that while simultaneous enhancement in the input and output beams is important for SECARS, the enhancement in the pump and anti-Stokes beams plays a more critical role in the overall enhancement than that in the Stokes beam. This work provides an insight into the enhancement mechanism of plasmon-enhanced spectroscopy, which is important for the design and optimization of plasmonic gratings. The PDG platform may also be applied to study enhancement mechanisms in other nonlinear light-matter interactions or the impact of plasmonic gratings on the fluorescence lifetime.

physics.optics↗

arXiv2020

Coherent Dynamics of the Off-Diagonal Spin-Boson Model in the Ultra-Strong Coupling Regime

Quantum mechanics describes the unitary time evolution of closed systems. In practice, every quantum system interacts with the environment leading to an irreversible loss of coherence. The Spin-Boson model (SBM) is central to the understanding of the fundamental process of decoherence of a two-state quantum system interacting with a bosonic heat bath but the nature of transient dynamics in the presence of hybrid diagonal and off-diagonal system-bath interactions remains largely unexplored. Here, we investigate how the hybrid system-bath interactions of an Ohmic environment induce localization in the bias-free SBM. For strong coupling to the environment, localization is strongly affected by a dynamically generated bias via the renormalization of the tunneling amplitude. We find that counteractive effects of Hamiltonian parameters on non-exponential short-time dynamics and long-time population equilibration can lead to a separation of timescales and non-equilibrium quantum coherent dynamics that can persist even for ultra-strong system-bath interaction. The findings offer novel opportunities to exploit coherence as a resource in quantum devices operating in the ultra-strong coupling regime.

physics.chem-ph↗

arXiv2018

Refining the Experimental Extraction of the Number of Independent Samples in a Mode-Stirred Reverberation Chamber

We investigate the number of independent samples in a chaotic reverberation chamber. Its evaluation as defined by the IEC standard can be made more precise when using not the index of the first value larger then the correlation length but using the value obtained by a linear interpolation instead. The results are validated by a juxtaposition with values from a measurement using a high stirrer-angle resolution. A comparison with estimates known from the literature validates our findings. An alternative approach using the local maxima of the parametric dependence of the transmission is presented in order to show the applicability of the extracted correlation length over a large range of frequencies.

physics.data-an↗

arXiv2018

Ultrafast Preparation and Detection of Ring Currents in Single Atoms

Quantum particles can penetrate potential barriers by tunneling (1). If that barrier is rotating, the tunneling process is modified (2,3). This is typical for electrons in atoms, molecules or solids exposed to strong circularly polarized laser pulses (4,5). Here we measure how the transmission probability through a rotating tunnel depends on the sign of the magnetic quantum number m of the electron and thus on the initial sense of rotation of its quantum phase. We further show that the electron keeps part of that rotary motion on its way through the tunnel by measuring m-dependent modification of the electron emission pattern. These findings are relevant for attosecond metrology as well as for interpretation of strong field electron emission from atoms and molecules (6-13) and directly demonstrates the creation of ring currents in bound states of ions with attosecond precision. In solids, this could open a way to inducing and controlling ring-current related topological phenomena (14).

physics.atom-ph↗

arXiv2017

Statistics of Reflection and Transmission in the Strong Overlap Regime of Fully Chaotic Reverberation Chambers

We have experimentally investigated a chaotic reverberation chamber in the regime of strong modal overlap ($1{<}d{<}150$) varying the opening as well as the coupling strength $κ$ of the two attached antennas. We find a good agreement with numerical distribution of the reflection $R=|S_{ii}|^2$ and transmission $T=|S_{21}|^2$ obtained via the effective Hamiltonian formalism using random matrix theory. The two parameters entering the numerics, $κ$ and the decay rate $τ$ were determined beforehand experimentally. Additionally we verified the relation predicted by Schroeder and Kuttruff for acoustic rooms between the averaged frequency spacing of maximal transmission $\langleδf_{max}\rangle$ and the decay rate.

cond-mat.dis-nn↗

arXiv2017

Introducing Enhanced Transport to the Effective Hamiltonian Approach via Random Matrices with a Pair of Connecting States

Direct transport processes play an important role in wireless communications where an ideal setup uses microwave fields to establish reliable communication channels between transmitter and receiver. But it is inherent to the problem that one cannot fully control the environment. While the influence of a complex scattering surrounding can be very well described using Random Matrix Theory it is not always obvious how to combine this universal approach with concrete communication channels. In this work we present an approach introducing an enhanced path between two antennas to the Hamilton operator to account for a prototypical problem. In order to be able to describe the stability of wireless chip-to-chip communication, we analyze the transport properties and predict the stability of the transmission under increasing importance of the environment.

cond-mat.dis-nn↗

arXiv2017

Fluctuations in an established transmission in the presence of a complex environment

In various situations where wave transport is preeminent, like in wireless communication, a strong established transmission is present in a complex scattering environment. We develop a novel approach to describe emerging fluctuations, which combines a transmitting channel and a chaotic background in a unified effective Hamiltonian. Modeling such a background by random matrix theory, we derive exact non-perturbative results for both transmission and reflection distributions at arbitrary absorption that is typically present in real systems. Remarkably, in such a complex scattering situation, the transport is governed by only two parameters: an absorption rate and the ratio of the so-called spreading width to the natural width of the transmission line. In particular, we find that the established transmission disappears sharply when this ratio exceeds unity. The approach exemplifies the role of the chaotic background in dephasing the deterministic scattering.

cond-mat.mes-hall↗

arXiv2017

Excitation of Nucleobases from a Computational Perspective II: Dynamics

This Chapter is devoted to unravel the relaxation processes taking place after photoexcitation of isolated DNA/RNA nucleobases in gas phase from a time-dependent perspective. To this aim, several methods are at hand, ranging from full quantum dynamics to various flavours of semiclassical or ab initio molecular dynamics, each with its advantages and its limitations. As this contribution shows, the most common approach employed up-to-date to learn about the deactivation of nucleobases in gas phase is a combination of the Tully surface hopping algorithm with on-the-fly CASSCF calculations. Different methods or, even more dramatically, different electronic structure methods can provide different dynamics. A comprehensive review of the different mechanisms suggested for each nucleobase is provided and compared to available experimental time scales. The results are discussed in a general context involving the effects of the different applied electronic structure and dynamics methods. Mechanistic similarities and differences between the two groups of nucleobases---the purine derivatives (adenine and guanine) and the pyrimidine derivatives (thymine, uracil, and cytosine)---are elucidated. Finally, a perspective on the future of dynamics simulations in the context of nucleobase relaxation is given.

physics.chem-ph↗

arXiv2017

Ultrafast Intersystem Crossing in SO$_2$ and Nucleobases

Mixed quantum-classical dynamics simulations show that intersystem crossing between singlet and triplet states in SO$_2$ and in nucleobases takes place on an ultrafast timescale (few 100~fs), directly competing with internal conversion.

physics.chem-ph↗