arXiv subjects

Tom J. P. Irons

Publications and source records attributed to Tom J. P. Irons.

8 recordsLinked to original sources

arXiv2026

Quantum Sensing for Spatial Spin Noise Mapping via Nitrogen-Vacancy Magnetic Quenching in Diamond

Detecting and mapping spin noise can reveal spatial variations in surface defect states, catalytic residues, free radicals, and spintronic materials. However, bulk measurements average over spatial heterogeneity, while scanning-probe maps require sequential rastering. Here, we demonstrate a microwave-free magnetic quenching (MQ) method for wide-field spin-noise mapping using nitrogen-vacancy (NV) centres in diamond. The protocol combines continuous LED illumination with a low-frequency, amplitude-modulated magnetic field, avoiding resonant microwave delivery or pulsed optical hardware. Field-induced spin-state mixing reduces NV photoluminescence, providing the primary contrast mechanism. We examine the response as a function of optical power and magnetic modulation amplitude, interpreting the results using a spin-state mixing model. The method is validated with aqueous gadobutrol concentration series, showing trends consistent with optically detected magnetic resonance (ODMR) measurements. We map spin-noise variations across boron nitride and single-walled carbon nanotube samples with differing defect and metallic catalyst contributions, supported by electron microscopy and spectroscopy. Notably, MQ detects a spin-noise response in boron nitride nanotubes that is silent in bulk EPR spectroscopy. This approach provides a practical framework for spatially resolved spin-noise sensing across quantum technologies and advanced functional materials.

physics.app-ph↗

arXiv2026

Polar Topologies in a Ferroelastic Metal Membrane

Polar metals, materials in which electric polarisation and metallicity coexist, are exceptionally rare because itinerant electrons screen long-range dipoles and favour centrosymmetric structures. Engineering polar textures in a conducting magnet holds promise for reconfigurable spin orbit coupling and magnetoelectric functionality. Here we show that releasing epitaxial SrRuO3 films from their substrates drives a hierarchy of ferroelastic domain refinement from micrometre to nanometre length scales, and that this structural reorganisation spontaneously generates two distinct classes of emergent polar texture that are ubiquitous across the freestanding membrane. Using correlative microscopy from mesoscale electron channelling contrast imaging (ECCI) to atomic resolution scanning transmission electron microscopy (STEM), we demonstrate that electric polarisation emerges selectively at translation-inequivalent antiphase boundaries (APBs). At these boundaries multicomponent aac tilt field undergoes Neel-like interpolation that preserves the in-phase tilt component and amplifies roto flexoelectric coupling, while translation-equivalent boundaries remain nonpolar. The Neel like interpolation at hard APBs and Ising like collapse of all tilt components at easy APBs is corroborated with ab initio calculations. While embedded 90 ferroelastic walls provide an additional mechanistically distinct source of electric polarisation resulting in polar nanoclusters (4 nm). These distinct nanotextures at 90 walls from via elastic accommodation of strain mismatch between variants and rotostriction as the tilt field interpolates across the boundaries. These findings show that, in a membrane form, metal oxides provide a robust platform for hosting nanoscale ferroelastic domains that generate polar textures.

cond-mat.mtrl-sci↗

arXiv2026

How Semilocal Are Semilocal Density Functional Approximations? -Tackling Self-Interaction Error in One-Electron Systems

Self-interaction error (SIE), arising from the imperfect cancellation of the spurious classical Coulomb interaction between an electron and itself, is a persistent challenge in modern density functional approximations. This issue is illustrated using the prototypical one-electron system $H_2^+$. While significant efforts have been made to eliminate SIE through the development of computationally expensive nonlocal density functionals, it is equally important to explore whether SIE can be mitigated within the framework of more efficient semilocal density functionals. In this study, we present a non-empirical meta-generalized gradient approximation (meta-GGA) that incorporates the Laplacian of the electron density. Our results demonstrate that the meta-GGA significantly reduces SIE, yielding a binding energy curve for $H_2^+$ that matches the exact solution at equilibrium and improves across a broad range of bond lengths over those of the Perdew-Burke-Ernzerhof (PBE) and strongly-constrained and appropriately-normed (SCAN) semilocal density functionals. This advancement paves the way for further development within the realm of semilocal approximations.

cond-mat.mtrl-sci↗

arXiv2025

Revisiting intrinsic spin defects in hexagonal boron nitride with r2SCAN

Hexagonal boron nitride (hBN) is a wide band gap, van der Waals material that is highly promising for solid-state quantum technologies as a host of optically addressable, paramagnetic spin defects. Intrinsic and extrinsic point defects provide a range of emission energies, but the atomic-level structures related to observed transitions are not fully characterised. In this work, intrinsic point defects in bulk hBN are modelled using density functional theory at the level of the meta-generalized gradient approximation (meta-GGA), considering their formation energies, electronic spectra and magnetic properties. The meta-GGA exchange-correlation functional r2SCAN is found to offer a balance between accuracy and computational efficiency for specific properties, while its predictive performance for bound-exciton stability is limited when compared to higher-level hybrid functionals. This implies opportunities for its use in optimised, hierarchical computational defect screening workflows. Under revised criteria, VB-, BN0, Bi+ and Ni+ defects are identified as stable colour centres with zero-phonon emission within technologically desirable wavelengths, making them promising for use in quantum networks and sensors.

quant-ph↗

arXiv2024

Coupling-Constant Averaged Exchange-Correlation Hole for He, Li, Be, N, Ne Atoms from CCSD

Accurate approximation of the exchange-correlation (XC) energy in density functional theory (DFT) calculations is essential for reliably modelling electronic systems. Many such approximations are developed from models of the XC hole; accurate reference XC holes for real electronic systems are crucial for evaluating the accuracy of these models however the availability of reliable reference data is limited to a few systems. In this study, we employ the Lieb optimization with a coupled cluster singles and doubles (CCSD) reference to construct accurate coupling-constant averaged XC holes, resolved into individual exchange and correlation components, for five spherically symmetric atoms: He, Li, Be, N, and Ne. Alongside providing a new set of reference data for the construction and evaluation of model XC holes, we compare our data against the exchange and correlation hole models of the established LDA and PBE density functional approximations. Our analysis confirms the established rationalization for the limitations of LDA and the improvement observed with PBE in terms of the hole depth and its long-range decay, demonstrated in real-space for the series of spherically-symmetric atoms.

physics.chem-ph↗

arXiv2023

Capturing the electron-electron cusp with the coupling-constant averaged exchange-correlation hole: A case study for Hooke's atoms

In density functional theory the exchange-correlation (XC) energy functional can be defined exactly through the coupling-constant ($λ$) averaged XC hole $\bar{n}_\text{xc}(\mathbf{r},\mathbf{r}')$, representing the probability depletion of finding an electron at $\mathbf{r}$ due to an electron at $\mathbf{r}$. Accurate knowledge of $\bar{n}_\text{xc}(\mathbf{r},\mathbf{r}')$ has been crucial for developing various XC energy density functional approximations and understanding their performance for real molecules and materials. However, there are very few systems for which accurate XC holes have been calculated, since this requires evaluating the one- and two-particle reduced density matrices for a reference wave function over a range of $λ$ whilst the electron density remains fixed at the physical ($λ=1$) density. Although the coupled-cluster singles and doubles (CCSD) method can yield exact results for a two-electron system in the complete basis set limit, it cannot capture the electron-electron cusp with commonly used finite basis sets. In this study, focusing on the Hooke's atom as a two-electron model system for which certain analytic solutions are known, we examine the effect of this cusp error on the XC hole calculated using CCSD. The Lieb functional is calculated at a range of coupling constants to determine the $λ$-integrated XC hole. Our results indicate that, for the Hooke's atoms, the error introduced by the description of the electron-electron cusp using Gaussian basis sets at the CCSD level is negligible compared to the basis set incompleteness error. The system-, angle- and coupling-constant-averaged XC hole is calculated using the same approach and provides a benchmark against which the Perdew-Burke-Ernzerhof (PBE) and local density approximation (LDA) XC hole models are assessed.

physics.chem-ph↗

arXiv2022

Exact constraints and appropriate norms in machine learned exchange-correlation functionals

Machine learning techniques have received growing attention as an alternative strategy for developing general-purpose density functional approximations, augmenting the historically successful approach of human designed functionals derived to obey mathematical constraints known for the exact exchange-correlation functional. More recently efforts have been made to reconcile the two techniques, integrating machine learning and exact-constraint satisfaction. We continue this integrated approach, designing a deep neural network that exploits the exact constraint and appropriate norm philosophy to deorbitalize the strongly constrained and appropriately normed SCAN functional. The deep neural network is trained to replicate the SCAN functional from only electron density and local derivative information, avoiding use of the orbital dependent kinetic energy density. The performance and transferability of the machine learned functional are demonstrated for molecular and periodic systems.

physics.chem-ph↗

arXiv2020

Robust All-Electron Optimization in Orbital-Free Density Functional Theory Using the Trust Region Image Method

We present a Gaussian-basis implementation of orbital-free density-functional theory (OF-DFT) in which the trust-region image method (TRIM) is used for optimization. This second-order optimization scheme has been constructed to provide benchmark all-electron results with very tight convergence of the particle number constraint, associated chemical potential and electron density. It is demonstrated that, by preserving the saddle-point nature of the optimization and simultaneously optimizing the density and chemical potential, an order of magnitude reduction in the number of iterations required for convergence is obtained. The approach is compared and contrasted with a new implementation of the nested optimization scheme put forward by Chan, Cohen and Handy. Our implementation allows for semi-local kinetic-energy (and exchange-correlation) functionals to be handled self-consistently in all-electron calculations. The all-electron Gaussian-basis setting for these calculations will enable direct comparison with a wide range of standard high-accuracy quantum-chemical methods as well as with Kohn-Sham density-functional theory. We expect that the present implementation will provide a useful tool for analysing the performance of approximate kinetic-energy functionals in finite systems.

physics.chem-ph↗