SearcharxivSearch

arXiv subjects

Simone Calvello

Publications and source records attributed to Simone Calvello.

4 recordsLinked to original sources

Finite-Temperature Toroidal Moment Amenable to Direct Observation in an Fe$_{10}$Dy$_{10}$ Molecular Ring

Single-molecule toroics (SMTs) host closed magnetic-vortex configurations that carry toroidal moments $\boldsymbol{\tau}$, whose electric-dipole symmetry enables magnetoelectric spin control. Yet, opposite toroidal chiralities are degenerate in conventional magnetic fields, making direct detection of molecular toroidal polarisation challenging. Current approaches probe molecular toroidal dynamics only indirectly through weak residual magnetism, leaving direct interrogation of toroidal polarisation an open challenge. Moreover, the survival of toroidal polarization at finite temperature, and realistic preparation-and-readout conditions, have not been quantitatively established. Here we investigate the icosanuclear $3d$--$4f$ molecular ring Fe$_{10}$Dy$_{10}$, featuring a $\sim$62-billion-dimensional low-energy manifold with pervasive toroidal character, rendered computationally tractable via an ab initio-informed transfer-matrix framework with perturbative corrections. Our model reproduces magnetic and calorimetric measurements and reveals a maximally toroidal ground doublet with robust finite-temperature toroidal response. We introduce the toroidal susceptibility $\xi$ as a finite-temperature linear-response function to quantify toroidal polarisation induced by magnetic-field curl. We then develop a preparation-and-detection protocol in which a temporally asymmetric near-infrared waveform generates a cumulative toroidal population imbalance, while an ab initio-informed magnetoelectric tensor predicts an electric-field-induced magnetic moment within $\mu$SQUID detectability. These results establish Fe$_{10}$Dy$_{10}$ as a molecular platform where toroidal polarisation can be prepared, accumulated and read out under realistic experimental conditions.

cond-mat.mes-hall

CERES: An ab initio code dedicated to the calculation of the electronic structure and magnetic properties of lanthanide complexes

We have developed and implemented a new ab initio code, CERES (Computational Emulator of Rare Earth Systems), completely written in C++11, which is dedicated to the efficient calculation of the electronic structure and magnetic properties of the crystal field states arising from the splitting of the ground state spin-orbit multiplet in lanthanide complexes. The new code gains efficiency via an optimised implementation of a direct configurational averaged Hartree-Fock (CAHF) algorithm for the determination of $4f$ quasi-atomic active orbitals common to all multi-electron spin manifolds contributing to the ground spin-orbit multiplet of the lanthanide ion. The new CAHF implementation is based on quasi-Newton convergence acceleration techniques coupled to an efficient library for the direct evaluation of molecular integrals, and problem-specific density matrix guess strategies. After describing the main features of the new code, we compare its efficiency with the current state--of--the--art ab initio strategy to determine crystal field levels and properties, and show that our methodology, as implemented in CERES, represents a more time-efficient computational strategy for the evaluation of the magnetic properties of lanthanide complexes, also allowing a full representation of non-perturbative spin-orbit coupling effects.

cond-mat.str-el

Room temperature chiral discrimination in paramagnetic NMR spectroscopy

A recently proposed theory of chiral discrimination in NMR spectroscopy based on the detection of a molecular electric polarization $\mathbf{P}$ rotating in a plane perpendicular to the NMR magnetic field [A. D. Buckingham, J. Chem. Phys. $\mathbf{140}$, 011103 (2014)], is here generalized to paramagnetic systems. Our theory predicts new contributions to $\mathbf{P}$, varying as the square of the inverse temperature. Ab initio calculations for ten Dy$^{3+}$ complexes, at 293K, show that in strongly anisotropic paramagnetic molecules $\mathbf{P}$ can be more than 1000 times larger than in diamagnetic molecules, making paramagnetic NMR chiral discrimination amenable to room temperature detection.

physics.chem-ph

Configuration-averaged 4f orbitals in ab initio calculations of low-lying crystal field levels in lanthanide(III) complexes

A successful and commonly used ab initio method for the calculation of crystal field levels and magnetic anisotropy of lanthanide complexes consists of spin-adapted state-averaged CASSCF calculations followed by state interaction with spin-orbit coupling (SI-SO). Based on two observations valid for Ln(III) complexes, namely: (i) CASSCF 4f orbitals are expected to change very little when optimized for different states belonging to the 4f electronic configuration, (ii) due to strong spin-orbit coupling the total spin is not a good quantum number, we show here via a straightforward analysis and direct calculation that the CASSCF/SI-SO method can be simplified to a single configuration-averaged HF calculation and one complete active space CI diagonalization, including spin-orbit coupling, on determinant basis. Besides its conceptual simplicity, this approach has the advantage that all spin states of the 4f$^n$ configuration are automatically included in the SO coupling, thereby overcoming one of the computational limitations of the existing CASSCF/SI-SO approach. As an example, we consider three isostructural complexes [Ln(acac)$_3$(H$_2$O)$_2$], Ln = Dy$^{3+}$, Ho$^{3+}$, Er$^{3+}$, and find that the proposed simplified method yields crystal field levels and magnetic g-tensors that are in very good agreement with those obtained with CASSCF/SI-SO.

physics.chem-ph