arXiv subjects

Alexei Nefedov

Publications and source records attributed to Alexei Nefedov.

7 recordsLinked to original sources

arXiv2026

Open-Shell Molecules as Sensitive Probes of Spin-Orbit-Controlled Surface Electronic Structure

Open-shell molecules are highly sensitive probes of correlated oxide surfaces because their partially occupied frontier orbitals strongly amplify subtle changes in adsorbate-substrate hybridization. Combining infrared reflection-absorption spectroscopy with hybrid density functional theory including non-collinear magnetism and spin-orbit coupling, we show that inclusion of spin-orbit coupling is essential to reproduce the vibrational spectrum of NO adsorbed on UO$_2$(111) by suppressing an otherwise artificial overhybridization between the NO frontier orbitals and uranium 5f states. While spin-orbit coupling determines the position of the N-O stretching and, dispersion-driven intermolecular interactions account for its asymmetric broadening at monolayer coverage. These results establish open-shell molecules as sensitive probes of spin-orbit-controlled surface electronic structure and identify NO/UO$_2$(111) as a stringent benchmark for electronic-structure methods describing open-shell molecule-surface interactions.

cond-mat.mtrl-sci↗

arXiv2024

Polarization-dependent effects in vibrational absorption spectra of 2D finite-size adsorbate islands on dielectric substrates

In the last years, Infrared Reflection-Absorption Spectroscopy (IRRAS) became a standard technique to study vibrational excitations of molecules. These investigations are strongly motivated by perspective applications in monitoring chemical processes. For a better understanding of the adsorption mechanism of molecules on dielectrics, the polarization-dependence of an interaction of infrared light with adsorbates at dielectric surfaces is commonly used. Thus, the peak positions in absorption spectra could be different for s- and p-polarized light. This shift between the peak positions depends on both the molecule itself and the dielectric substrate. While the origin of this shift is well understood for infinite two-dimensional adsorbate layers, finite-size samples, which consist of 2D islands of a small number of molecules, have never been considered. Here, we present a study on polarization-dependent finite-size effects in the optical response of such islands on dielectric substrates. The study uses a multi-scale modeling approach that connects quantum chemistry calculations to Maxwell scattering simulations. We distinguish the optical response of a single molecule, a finite number of molecules, and a two-dimensional adsorbate layer. We analyze CO and CO$_2$ molecules deposited on CeO$_2$ and Al$_2$O$_3$ substrates. The evolution of the shift between the polarization-dependent absorbance peaks is firstly studied for a single molecule, which it does not exhibit for at all, and for finite molecular islands, which it increases with increasing island size for, as well as for an infinite two-dimensional adsorbate layer. In the latter case, the agreement between the obtained results and the experimental IRRAS data and more traditional three/four-layer-model theoretical studies supports the predictive power of the multi-scale approach.

physics.optics↗

arXiv2020

Vibrational Frequencies of Cerium Oxide-Bound CO: A Challenge for Conventional DFT Methods

In ceria-based catalysis, the shape of the catalyst particle, which determines the exposed crystal facets, profoundly affects its reactivity. The vibrational frequency of adsorbed carbon monoxide (CO) can be used as a sensitive probe to identify the exposed surface facets, provided reference data on well-defined single crystal surfaces together with a definitive theoretical assignment exist. We investigate the adsorption of CO on the CeO2(110 and (111) surfaces and show that the commonly applied DFT(PBE)+U method does not provide reliable CO vibrational frequencies by comparing with state-of-the-art infrared spectroscopy experiments for monocrystalline CeO2 surfaces. Good agreement requires the hybrid DFT approach with the HSE06 functional. The failure of conventional DFT is explained in terms of its inability to accurately describe the facet- and configuration-specific donation and backdonation effects that control the changes in the C-O bond length upon CO adsorption and the CO force constant. Our findings thus provide a theoretical basis for the detailed interpretation of experiments and open up the path to characterize more complex scenarios, including oxygen vacancies and metal adatoms.

cond-mat.mtrl-sci↗

arXiv2008

Dose dependence of ferromagnetism in Co-implanted ZnO

We have studied the structural, magnetic and electronic properties of Co-implanted ZnO (0001) films grown on Al2O3 (1120) substrates for different implantation doses and over a wide temperature range. Strong room temperature ferromagnetism is observed with magnetic parameters depending on the cobalt implantation dose. A detailed analysis of the structural and magnetic properties indicates that there are two magnetic phases in Co-implanted ZnO films. One is a ferromagnetic phase due to the formation of long range ferromagnetic ordering between implanted magnetic cobalt ions in the ZnO layer, the second one is a superparamagnetic phase, which occurs due to the formation of metallic cobalt clusters in the Al2O3 substrate. Using x-ray resonant magnetic scattering, the element specific magnetization of cobalt, oxygen and Zn was investigated. Magnetic dichroism was observed at the Co L2,3 edges as well as at the O K edge. In addition, the anomalous Hall effect is also observed, supporting the intrinsic nature of ferromagnetism in Co-implanted ZnO films.

cond-mat.mtrl-sci↗

arXiv2008

High temperature ferromagnetism in Co-implanted TiO2 rutile

We report on structural, magnetic and electronic properties of Co-implanted TiO2 rutile single crystals for different implantation doses. Strong ferromagnetism at room temperature and above is observed in TiO2 rutile plates after cobalt ion implantation, with magnetic parameters depending on the cobalt implantation dose. While the structural data indicate the presence of metallic cobalt clusters, the multiplet structure of the Co L3 edge in the XAS spectra gives clear evidence for a substitutional Co 2+ state. The detailed analysis of the structural and magnetic properties indicates that there are two magnetic phases in Co-implanted TiO2 plates. One is a ferromagnetic phase due to the formation of long range ferromagnetic ordering between implanted magnetic cobalt ions in the rutile phase, and the second one is a superparamagnetic phase originates from the formation of metallic cobalt clusters in the implanted region. Using x-ray resonant magnetic scattering, the element specific magnetization of cobalt, oxygen and titanium in Co-implanted TiO2 single crystals are investigated. Magnetic dichroism was observed at the Co L edges as well as at the O K edge. The interaction mechanism, which leads to ferromagnetic ordering of substituted cobalt ions in the host matrix, is also discussed.

cond-mat.mtrl-sci↗

arXiv2008

Intrinsic room temperature ferromagnetism in Co-implanted ZnO

We report on the structural and magnetic properties of a cobalt-implanted ZnO film grown on a sapphire substrate. X-ray diffraction and transmission electron microscopy reveal the presence of a (10-10)-oriented hexagonal Co phase in the Al2O3 sapphire substrate, but not in the ZnO film. Co clusters, with a diameter of is about 5-6 nm, form a Co rich layer in the substrate close to the ZnO/Al2O3 interface. Magnetization measurements indicate that there exist two different magnetic phases in the implanted region. One originates from the Co clusters in Al2O3, the other one belongs to a homogeneous ferromagnetic phase with a ferromagnetic Curie temperature far above room temperature and can be attributed to Co substitution on Zn sites in the ZnO layer. We have observed magnetic dichroism at the Co L2,3 and O K edges at room temperature as well as the multiplet structure in x-ray absorption spectra around the Co L3 edge, supporting the intrinsic nature of the observed ferromagnetism in Co-implanted ZnO film. The magnetic moment per substituted cobalt is found about 2.81 Bohr magneton which is very close to the theoretical expected value of 3 Bohr magneton per Co atom for Co 2+ in its high spin state.

cond-mat.mtrl-sci↗

arXiv2005

Soft X-ray Resonant Magnetic Scattering Studies on Fe/CoO Exchange Bias System

We have used soft X-ray Resonant Magnetic Scattering (XRMS) to search for the presence of an effective ferromagnetic moment belonging to the antiferromagnetic (AF) layer which is in close contact with a ferromagnetic (F) layer. Taking advantage of the element specificity of the XRMS technique, we have measured hysteresis loops of both Fe and CoO layers of a CoO(40 Å)/Fe(150 Å) exchange bias bilayer. From these measurements we have concluded that the proximity of the F layer induces a magnetic moment in the AF layer. The F moment of the AF layer has two components: one is frozen and does not follow the applied magnetic field and the other one follows in phase the ferromagnetic magnetization of the F layer. The temperature dependence of the F components belonging to the AF layer is shown and discussed.

cond-mat.mtrl-sci↗