arXiv subjects

H. Appel

Publications and source records attributed to H. Appel.

10 recordsLinked to original sources

arXiv2022

First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images

Tip-enhanced Raman scattering (TERS) has emerged as a powerful tool to obtain subnanometer spatial resolution fingerprints of atomic motion. Theoretical calculations that can simulate the Raman scattering process and provide an unambiguous interpretation of TERS images often rely on crude approximations of the local electric field. In this work, we present a novel and first principles-based method to compute TERS images by combining Time-Dependent Density Functional Theory (TD-DFT) and Density Functional Perturbation Theory (DFPT) to calculate Raman cross sections with realistic local fields. We present TERS results on the benzene and TCNE molecule, the latter of which is adsorbed at Ag(110). We demonstrate that chemical effects on chemisorbed molecules, often ignored in TERS simulations of medium and large systems sizes, dramatically change TERS images. This calls for the inclusion of chemical effects for predictive theory-experiment comparisons and understanding of molecular motion at the nanoscale.

physics.chem-ph↗

arXiv2015

Many-body Green's function theory for electron-phonon interactions: the Kadanoff-Baym approach to spectral properties of the Holstein dimer

We present a Kadanoff-Baym formalism to study time-dependent phenomena for systems of interacting electrons and phonons in the framework of many-body perturbation theory. The formalism takes correctly into account effects of the initial preparation of an equilibrium state, and allows for an explicit time-dependence of both the electronic and phononic degrees of freedom. The method is applied to investigate the charge neutral and non-neutral excitation spectra of a homogeneous, two-site, two-electron Holstein model. This is an extension of a previous study of the ground state properties in the Hartree (H), partially self-consistent Born (Gd) and fully self-consistent Born (GD) approximations published in Ref. [arXiv:1403.2968]. We show that choosing a homogeneous ground state solution leads to unstable dynamics for a sufficiently strong interaction, and that allowing a symmetry-broken state prevents this. The instability is caused by the bifurcation of the ground state and understood physically to be connected with the bipolaronic crossover of the exact system. This mean-field instability persists in the partially self-consistent Born approximation but is not found for the fully self-consistent Born approximation. By understanding the stability properties, we are able to study the linear response regime by calculating the density-density response function by time-propagation. This functions amounts to a solution of the Bethe-Salpeter equation with a sophisticated kernel. The results indicate that none of the approximations is able to describe the response function during or beyond the bipolaronic crossover for the parameters investigated. Overall, we provide an extensive discussion on when the approximations are valid, and how they fail to describe the studied exact properties of the chosen model system.

cond-mat.mes-hall↗

arXiv2014

Many-body Green's function theory for electron-phonon interactions: ground state properties of the Holstein dimer

We study ground-state properties of a two-site, two-electron Holstein model describing two molecules coupled indirectly via electron-phonon interaction by using both exact diagonalization and self-consistent diagrammatic many-body perturbation theory. The Hartree and self-consistent Born approximations used in the present work are studied at different levels of self-consistency. The governing equations are shown to exhibit multiple solutions when the electron-phonon interaction is sufficiently strong whereas at smaller interactions only a single solution is found. The additional solutions at larger electron-phonon couplings correspond to symmetry-broken states with inhomogeneous electron densities. A comparison to exact results indicates that this symmetry breaking is strongly correlated with the formation of a bipolaron state in which the two electrons prefer to reside on the same molecule. The results further show that the Hartree and partially self-consistent Born solutions obtained by enforcing symmetry do not compare well with exact energetics, while the fully self-consistent Born approximation improves the qualitative and quantitative agreement with exact results in the same symmetric case. This together with a presented natural occupation number analysis supports the conclusion that the fully self-consistent approximation describes partially the bipolaron crossover. These results contribute to better understanding how these approximations cope with the strong localizing effect of the electron-phonon interaction.

cond-mat.str-el↗

arXiv2012

Ab-initio angle and energy resolved photoelectron spectroscopy with time-dependent density-functional theory

We present a time-dependent density-functional method able to describe the photoelectron spectrum of atoms and molecules when excited by laser pulses. This computationally feasible scheme is based on a geometrical partitioning that efficiently gives access to photoelectron spectroscopy in time-dependent density-functional calculations. By using a geometrical approach, we provide a simple description of momentum-resolved photoe- mission including multi-photon effects. The approach is validated by comparison with results in the literature and exact calculations. Furthermore, we present numerical photoelectron angular distributions for randomly oriented nitrogen molecules in a short near infrared intense laser pulse and helium-(I) angular spectra for aligned carbon monoxide and benzene.

physics.atom-ph↗

arXiv2011

Time-dependent density-functional and reduced density-matrix methods for few electrons: Exact versus adiabatic approximations

To address the impact of electron correlations in the linear and non-linear response regimes of interacting many-electron systems exposed to time-dependent external fields, we study one-dimensional (1D) systems where the interacting problem is solved exactly by exploiting the mapping of the 1D $N$-electron problem onto an $N$-dimensional single electron problem. We analyze the performance of the recently derived 1D local density approximation as well as the exact-exchange orbital functional for those systems. We show that the interaction with an external resonant laser field shows Rabi oscillations which are detuned due to the lack of memory in adiabatic approximations. To investigate situations where static correlations play a role, we consider the time-evolution of the natural occupation numbers associated to the reduced one-body density matrix. Those studies shed light on the non-locality and time-dependence of the exchange and correlation functionals in time-dependent density and density-matrix functional theories.

cond-mat.other↗

arXiv2008

Time-dependent natural orbitals and occupation numbers

We report equations of motion for the occupation numbers of natural spin orbitals and show that adiabatic extensions of common functionals employed in ground-state reduced-density-matrix-functional theory have the shortcoming of leading always to occupation numbers which are independent of time. We illustrate the exact time-dependence of the natural spin orbitals and occupation numbers for the case of electron-ion scattering and for atoms in strong laser fields. In the latter case, we observe strong variations of the occupation numbers in time.

cond-mat.mtrl-sci↗

arXiv2005

Measuring the kernel of time-dependent density functional theory with X-ray absorption spectroscopy of 3d transition metals

The 2p-3d core hole interaction in the L2,3 absorption spectra of the 3d transition metals is treated within time-dependent density functional theory (TDDFT). A simple three-level model explains the origin of the strong deviations from the one-particle branching ratio and yields matrix elements of the unknown exchange-correlation (XC) kernel directly from experiment.

cond-mat.mtrl-sci↗

arXiv2005

Double-Pole Approximation in Time-Dependent Density Functional Theory

A simple approximate solution to the linear response equations of time-dependent density functional theory (TDDFT) is given. This extends the single-pole approximation (SPA) to two strongly-coupled poles. The analysis provides both an illustration of how TDDFT works when strong exchange-correlation effects are present and insight into such corrections. For example, interaction can cause a transition to vanish entirely from the optical spectrum.

cond-mat.mtrl-sci↗

arXiv2005

Operation of a Bloch oscillator

We report the operation of a Bloch oscillator. The active medium was a staticvoltage driven, doped GaAs/AlAs superlattice which was electromagnetically coupled to a resonator. The oscillator produced tuneable microwave radiation (frequency ~ 60 GHz; power ~ 0.5 mW; efficiency ~ 4 %). The gain (~ 10^4 /cm) was due to the nonlinearity mediated by miniband electrons. We also present a theory of the oscillator. The Bloch oscillator should in principle be feasible for generation of radiation up to frequencies of 10 THz and more.

cond-mat.mes-hall↗

arXiv2002

Excitations in time-dependent density-functional theory

An approximate solution to the time-dependent density functional theory (TDDFT) response equations for finite systems is developed, yielding corrections to the single-pole approximation. These explain why allowed Kohn-Sham transition frequencies and oscillator strengths are usually good approximations to the true values, and why sometimes they are not. The approximation yields simple expressions for Görling-Levy perturbation theory results, and a method for estimating expectation values of the unknown exchange-correlation kernel.

cond-mat.mtrl-sci↗