arXiv subjects

G. Gandus

Publications and source records attributed to G. Gandus.

3 recordsLinked to original sources

arXiv2023

Exchange interactions and intermolecular hybridization in a spin-1/2 nanographene dimer

Phenalenyl is a radical nanographene with triangular shape that hosts an unpaired electron with spin S = 1/2. The open-shell nature of phenalenyl is expected to be retained in covalently bonded networks. Here, we study a first step in that direction and report the synthesis of the phenalenyl dimer by combining in-solution synthesis and on-surface activation and its characterization both on Au(111) and on a monolayer of NaCl on top of Au(111) by means of inelastic electron tunneling spectroscopy (IETS). IETS shows inelastic steps that, together with a thorough theoretical analysis, are identified as the singlet-triplet excitation arising from interphenalenyl exchange. Two prominent features of our data permit to shed light on the nature of spin interactions in this system. First, the excitation energies with and without the NaCl decoupling layer are 48 and 41 meV, respectively, indicating a significant renormalization of the spin excitation energies due to exchange with the Au(111) electrons. Second, a position-dependent bias-asymmetry of the height of the inelastic steps is accounted for by an interphenalenyl hybridization of the singly occupied phenalenyl orbitals that is only possible via third neighbor hopping. This hybridization is also essential to activate kinetic interphenalenyl exchange. Our results set the stage for future work on the bottom-up synthesis of spin S = 1/2 spin lattices with large exchange interaction.

cond-mat.mes-hall↗

arXiv2022

Strongly correlated physics in organic open-shell quantum systems

Strongly correlated physics arises from electron-electron scattering within partially filled orbitals. Organic molecules in open-shell configurations are therefore good candidates to exhibit many-body effects. We focus on electron transport in a two-terminal single-molecule junction setup, in which the molecular bridge consists of an organic radical with a molecular orbital hosting a single unpaired electron (SOMO). We perform beyond state-of-the-art numerical simulations combining an ab-initio description of the chemical environment, with quantum field-theoretical techniques that account for many-body effects. The key observation is that the SOMO resonance is prone to splitting and we identify a giant electronic scattering rate as the driving many-body mechanism, akin to that of the Mott metal-to-insulator transition. By comparing linear and cyclic radicals, we show that the spatial distribution of the SOMO and its projection on the molecular backbone have dramatic consequences for the transport properties of the junction. We argue that the phenomenon and the underlying microscopic mechanism apply to a broad family of open-shell molecular systems, and can explain puzzling experimental observations such as suppressed conductance in radical junctions.

cond-mat.str-el↗

arXiv2020

Smart local orbitals for efficient calculations within density functional theory and beyond

Localized basis sets in the projector augmented wave formalism allow for computationally efficient calculations within density functional theory (DFT). However, achieving high numerical accuracy requires an extensive basis set, which also poses a fundamental problem for the interpretation of the results. We present a way to obtain a reduced basis set of atomic orbitals through the subdiagonalization of each atomic block of the Hamiltonian. The resulting local orbitals (LOs) inherit the information of the local crystal field. In the LO basis, it becomes apparent that the Hamiltonian is nearly block-diagonal, and we demonstrate that it is possible to keep only a subset of relevant LOs which provide an accurate description of the physics around the Fermi level. This reduces to some extent the redundancy of the original basis set, and at the same time it allows one to perform post-processing of DFT calculations, ranging from the interpretation of electron transport to extracting effective tight-binding Hamiltonians, very efficiently and without sacrificing the accuracy of the results.

cond-mat.mtrl-sci↗