arXiv subjects

Giulia Galli

Publications and source records attributed to Giulia Galli.

At least 19 recordsLinked to original sources

arXiv2026

Optical decoherence in Er$^{3+}$-doped CeO$_2$ spin qubit platforms

Erbium ions (Er$^{3+}$) in cerium dioxide (CeO$_2$) represent a promising spin-photon interface for quantum communication, but the mechanisms limiting their optical coherence remain poorly understood. Using periodic hybrid density functional theory calculations with finite-size corrections, we identify Ce$^{3+}$ polarons and their complexes with oxygen vacancies and Er$^{3+}$ dopants as likely sources of optical decoherence. These defects exhibit finite photoionization cross-sections at 0.8 eV, coinciding with both the laser excitation energy used experimentally and the emission energy of Er$^{3+}$. This resonance enables photoionization of the polarons and photoluminescence quenching of Er$^{3+}$, leading to the broadening of optical linewidths, shortening of excited-state lifetimes, and introduction of charge noise. Our concentration-dependent photocurrent measurements in Er$^{3+}$-doped CeO$_2$ films under 0.8 eV illumination validate the predicted decoherence pathway. Our combined computational and experimental results identify a concrete defect-engineering target for improving the Er$^{3+}$-doped CeO$_2$ platform, and point to a decoherence mechanism likely relevant to other Er$^{3+}$-doped multivalent-oxide quantum platforms.

cond-mat.mtrl-sci↗

arXiv2026

First-principles cumulant approach to the vibronic structure of spin defects

Color centers in wide-band-gap semiconductors are leading platforms for solid-state quantum technologies, yet a quantitative description of their vibronic structure has remained elusive due to the complexity of multi-phonon processes in localized defect states. Here we present a first-principles Green's function framework based on the retarded cumulant ansatz (RCA) to describe electron-phonon interactions in spin defects; our approach goes beyond the adiabatic and lowest-order perturbation theory approximations underlying widely used approaches. Applied to the negatively charged nitrogen-vacancy (NV$^-$) center in diamond, our method reveals that multi-phonon satellites persist over a 400 meV energy window even at zero temperature, driven by quantum zero-point fluctuations. We demonstrate that accurate spectral functions require mode-, momentum-, spin-, and orbital-resolved electron-phonon matrix elements sampled across the full Brillouin zone, to account for hybridized and propagating phonon channels. We find that the vibronic structure of the NV$^-$ center exhibits strong spin and orbital anisotropy, with different orbitals coupling to qualitatively distinct parts of the phonon spectrum, and spin-selective coupling affecting both sideband positions and intensities.

cond-mat.mtrl-sci↗

arXiv2026

Nitrogen Vacancy Centers in Hexagonal Diamond Exhibit Long Coherence Times

We show that negatively charged nitrogen-vacancy (NV) centers in the hexagonal diamond polymorph lonsdaleite offer a route to spin qubits with enhanced coherence relative to their cubic-diamond counterparts. Using first-principles calculations, we examine two distinct defect configurations, AA, with the same symmetry as in cubic diamond and AB, with reduced symmetry. We find that the AB configuration of the NV center exhibits a finite transverse zero-field splitting, giving rise to an approximate fourfold enhancement of the Hahn-echo coherence time $T_2$ at zero magnetic field. The AA configuration, by contrast, closely reproduces the electronic structure and coherence properties of the cubic NV center. We further characterize the many-body electronic structure, vertical excitation energies, and photoluminescence spectra of both configurations, providing spectral fingerprints for their experimental identification. Our results establish symmetry-broken NV centers in lonsdaleite as promising candidates for quantum sensing and information science applications.

cond-mat.mtrl-sci↗

arXiv2026

A First-principles Computational Framework for Quantum Decoherence in Complex Diamond Spin Environments

Quantum decoherence induced by defects remains a major limitation for solid-state quantum technologies, yet predicting decoherence in realistic materials remains computationally challenging. Complex defect populations are often approximated as homogeneous spin baths, obscuring the role of defect-specific electronic structure and spin dynamics. Here, we develop a predictive framework for decoherence in diamond by combining first-principles electronic-structure calculations, quantum many-body spin-bath simulations, and experimental validation. The framework incorporates defect-resolved spin Hamiltonians and heterogeneous spin baths containing multiple paramagnetic defect species. Using diamond nitrogen-vacancy ensembles as a model platform, we investigate mixed nitrogen-, vacancy-, and hydrogen-related defect environments. We show that decoherence depends not only on defect density but also on defect identity and bath composition, whose distinct electronic structures, hyperfine interactions, and spin dynamics produce different coherence behavior. Heterogeneous defect populations can either suppress or enhance decoherence, producing trends unexplained by homogeneous-bath models. Magnetic-field-dependent Hahn-echo measurements on samples with different defect concentrations validate the framework. The calculations reproduce the observed coherence times and stretched-exponential decay behavior across a broad magnetic-field range and identify vacancy-related defects as critical contributors beyond the conventionally assumed P1 spin bath. By linking atomistic defect properties to quantum coherence, our framework provides a predictive route for identifying hidden defect environments and optimizing decoherence in defect-based quantum materials.

quant-ph↗

arXiv2026

Analytical Forces from the Bethe-Salpeter Equation for Large-Scale Excited-State Relaxation

We present an efficient plane-wave implementation of analytical nuclear forces for electronic excited states described by the Bethe-Salpeter equation (BSE). The formulation combines density-matrix perturbation theory with a Lagrangian approach, and avoids both explicit empty-state summations and the response calculations for each atomic displacement, required by conventional approaches based on density functional perturbation theory. Together with GPU acceleration, these advances make BSE forces calculations tractable for solid-state systems containing hundreds of atoms. We demonstrate the method on two point defects with distinct dielectric environments: the nitrogen-vacancy center in diamond, where BSE and time-dependent density functional theory (TDDFT) yield consistent excited-state relaxations, and the carbon-dimer defect in two-dimensional hexagonal boron nitride, where the screened electron-hole interaction included in the BSE stabilizes the localized defect excitation and corrects the relaxation pattern predicted by semilocal TDDFT. These results establish a scalable framework for BSE-level studies of excited-state relaxation and vibronic coupling in heterogeneous condensed systems.

cond-mat.mtrl-sci↗

arXiv2026

Multireference Density Matrix Embedding for Spin-Phonon Relaxation

Spin-phonon coupling governs magnetic relaxation in numerous systems including single-molecule magnets and molecular spin qubits. In most cases, the accurate prediction of spin relaxation rates requires multireference electronic structure methods, but their computational cost has largely restricted such calculations to isolated molecules. Here we show that spin-phonon relaxation rates can be computed within a multireference density matrix embedding framework. We apply the approach to three cobalt- and two dysprosium-based single-molecule magnets and to a cobalt-based molecular crystal. Across all systems, treating only the first coordination sphere of the magnetic center at the multireference level reproduces spin relaxation rates in good agreement with non-embedded CASSCF calculations while reducing the correlated problem to 10-68% of the total basis functions. Periodic calculations further demonstrate that spin relaxation rates can be computed for a molecular crystal using an embedded active space of only 259 basis functions out of a total of 2569. These results show that multireference density matrix embedding extends quantitative spin-phonon relaxation calculations from isolated molecules to molecular crystals.

physics.chem-ph↗

arXiv2026

The WEST code for large-scale excited-state materials simulations

We present WEST, an open-source plane-wave pseudopotential code for large-scale excited-state materials simulations, and describe its theoretical foundations, software architecture, and capabilities. WEST implements full-frequency GW, quantum defect embedding theory, the Bethe-Salpeter equation, and time-dependent density functional theory within a common algorithmic framework that avoids the explicit computation of virtual electronic states. By combining density functional and density matrix perturbation theory, low-rank representations of the dielectric screening and exact exchange, and localization techniques, WEST achieves favorable computational scaling with system size. The code supports the calculation of quasi-particle and neutral excitation energies, optical and photoluminescence spectra, excited-state forces, and non-adiabatic couplings, with interoperable workflows connecting to quantum chemistry, vibronic coupling, and quantum computing packages. A hierarchical parallelization strategy and GPU acceleration deliver near-ideal strong scaling to thousands of GPUs, enabling accurate excited-state simulations of systems with more than a thousand atoms. Representative applications, spanning the full optical cycle of solid-state spin defects, self-trapped excitons in metal-halide perovskites, and the optical response of liquid water and ice, demonstrate the accuracy and versatility of the code across diverse material classes. The capabilities implemented in WEST establish the code as a scalable platform for predictive excited-state simulations, high-throughput materials discovery, and the generation of high-fidelity datasets for machine learning in computational materials science.

cond-mat.mtrl-sci↗

arXiv2026

Large-scale first-principle simulations of amorphous indium oxide

Amorphous indium oxide (a-In$_2$O$_3$) is a high-electron-mobility semiconductor of central importance in thin-film transistors and a promising photoanode for solar-driven water oxidation. Despite sustained experimental and computational investigations, the structural motifs underlying its unusual transport properties and the existence of O-O peroxide-like bonds within its network have remained unresolved. Here we develop a MACE-based machine-learned interatomic potential trained on first-principles molecular dynamics trajectories and use it to generate and analyze amorphous structures containing up to 5120 atoms, two orders of magnitude larger than those adopted in typical ab initio studies. We find X-ray structure factors in excellent quantitative agreement with experiment and we confirm that In$_2$O$_3$ is a poor glass former, with the likely presence of quasi-crystalline regions in amorphous samples. Our large-scale structural analysis reveals extended chains of edge-sharing InO$_k$ polyhedra providing a concrete structural basis for the high electron mobility of a-In$_2$O$_3$. Our results strongly support the formation of O-O peroxide-like bonds in the amorphous network, with a mean length of 1.5 \AA{}. We show that these bonds introduce localized in-gap states near the conduction band minimum, acting as a source of intrinsic n-type self-doping and enhancing sub-gap optical absorption. These effects are detectable via a distinct Raman feature near 850 cm$^{-1}$ that is absent in the IR spectrum. Overall, our results establish a comprehensive structure-property picture of a-In$_2$O$_3$, provide directly testable experimental predictions, and suggest that controlled amorphization is a viable strategy for improving the photoelectrochemical activity of a-In$_2$O$_3$.

cond-mat.mtrl-sci↗

arXiv2026

First-principles calculations of internal conversion processes in spin defects

Optically active spin defects are foundational for quantum technologies, yet common approximations underestimate their internal conversion (IC) rates by orders of magnitude. We propose a broad, predictive framework to compute IC rates that incorporates multi-configurational effects via many-body wavefunctions in TDDFT, and includes all-phonon-mode contributions via analytical non-adiabatic couplings. Our approach resolves discrepancies with experiment, achieving quantitative agreement for the NV$^-$ center in diamond, and identifying a previously overlooked non-radiative channel in the divacancy triplet lifetime in SiC.

cond-mat.mtrl-sci↗

arXiv2026

Spin Dynamics from Atomistic Quantum Simulations

Optically active solid-state spin defects are promising candidates for quantum applications, however a unified theoretical framework to predict their spin dynamics at high temperatures is not yet available. Here, using Kubo linear--response theory, we derive expressions of spin-lattice and decoherence times $T_1$ and $T_2$ in terms of correlation functions of spin--lattice couplings. We then evaluate $T_1$ and $T_2$ from molecular dynamics and spin--lattice interaction time--series generated by state--of--the--art machine learning models trained on {\it ab--initio} data. Finally we measure $T_1$ times for the NV center in diamond and compare experimental and theoretical results, showing excellent agreement.

cond-mat.mtrl-sci↗

arXiv2025

Understanding Surface-Induced Decoherence of NV Centers in Diamond

Nitrogen vacancy centers (NV) in proximity to diamond surfaces are promising nanoscale quantum sensors. However, their coherence properties are negatively affected by magnetic and electric surface noise, whose origin and detailed impact have remained elusive. Using atomistic models of diamond surfaces derived with density functional theory, together with decoherence time calculations with cluster correlation expansion methods, we quantify the effects of surface crystallographic orientation and functionalization, and of the density of unpaired electrons on the NV Hahn-echo time $T_2$. We determine a crossover depth at which $T_2$ ceases to be limited by surface nuclear spins and recovers the bulk-limited value. We find that for static surface-electron baths, the ratio between the NV depth and the separation between surface electron spins determines a transition from fast-fluctuating to quasi-static noise, leading to a dependence of $T_2$ on orientation for specific surfaces. We also find that the modulation of $T_2$ by spin-phonon relaxations leads to motional-narrowing at sub-microsecond relaxation times. Importantly, our calculations show that it is only when accounting for surface-spin in-sequence hopping that measured $T_2$ values as a function of depth can be reproduced, thus highlighting the importance of hopping-mediated models to describe the surface spin noise affecting NV sensors. Overall, our work provides clear guidelines for engineering diamond surfaces to achieve enhanced NV coherence for quantum sensing and information processing applications.

quant-ph↗

arXiv2025

Characterizing Defect Dynamics in Silicon Carbide Using Symmetry-Adapted Collective Variables and Machine Learning Interatomic Potentials

Silicon carbide (SiC) divacancies are attractive candidates for spin defect qubits possessing long coherence times and optical addressability. The high activation barriers associated with SiC defect formation and motion pose challenges for their study by first-principles molecular dynamics. In this work, we develop and deploy machine learning interatomic potentials (MLIPs) to accelerate defect dynamics simulations while retaining ab initio accuracy. We employ an active learning strategy comprising symmetry-adapted collective variable discovery and enhanced sampling to compile configurationally diverse training data, calculation of energies and forces using density functional theory (DFT), and training of an E(3)-equivariant MLIP based on the Allegro model. The trained MLIP reproduces DFT-level accuracy in defect transition activation free energy barriers, enables the efficient and stable simulation of multi-defect 216-atom supercells, and permits an analysis of the temperature dependence of defect thermodynamic stability and formation/annihilation kinetics to propose an optimal annealing temperature to maximally stabilize VV divacancies.

cond-mat.mtrl-sci↗

arXiv2025

Elucidating the Inter-system Crossing of the Nitrogen-Vacancy Center up to Megabar Pressures

The integration of Nitrogen-Vacancy color centers into diamond anvil cells has opened the door to quantum sensing at megabar pressures. Despite a multitude of experimental demonstrations and applications ranging from quantum materials to geophysics, a detailed microscopic understanding of how stress affects the NV center remains lacking. In this work, using a combination of first principles calculations as well as high-pressure NV experiments, we develop a complete description of the NV's optical properties under general stress conditions. In particular, our ab initio calculations reveal the complex behavior of the NV's inter-system crossing rates under stresses that both preserve and break the defect's symmetry. Crucially, our proposed framework immediately resolves a number of open questions in the field, including: (i) the microscopic origin of the observed contrast-enhancement in (111)-oriented anvils, and (ii) the surprising observation of NV contrast-inversion in certain high-pressure regimes. Our work lays the foundation for optimizing the performance of NV high-pressure sensors by controlling the local stress environment, and more generally, suggests that symmetry-breaking stresses can be utilized as a novel tuning knob for generic solid-state spin defects.

quant-ph↗

arXiv2025

Strategies to search for two-dimensional materials with long spin qubit coherence time

Two-dimensional (2D) materials that can host qubits with long spin coherence time (T2) have the distinct advantage of integrating easily with existing microelectronic and photonic platforms, making them attractive for designing novel quantum devices with enhanced performance. However, the relative lack of 2D materials as spin qubit hosts, as well as appropriate substrates that can help maintain long T2, necessitates a strategy to search for candidates with robust spin coherence. Here, we develop a high-throughput computational workflow to predict the nuclear spin bath-driven qubit decoherence and T2 in 2D materials and heterostructures. We initially screen 1173 2D materials and find 190 monolayers with T2 > 1 ms, higher than that of naturally-abundant diamond. We then construct 1554 lattice-commensurate heterostructures between high-T2 2D materials and select 3D substrates, and we find that T2 is generally lower in a heterostructure than in the bare 2D host material; however, low-noise substrates (such as CeO2 and CaO) can help maintain high T2. To further accelerate the material screening effort, we derive analytical models that enable rapid predictions of T2 for 2D materials and heterotructures. The models offer a simple, yet quantitative, way to determine the relative contributions to decoherence from the nuclear spin baths of the 2D host and substrate in a heterostructural system. By developing a high-throughput workflow and analytical models, we expand the genome of 2D materials and their spin coherence times for the development of spin qubit platforms.

quant-ph↗

arXiv2025

Spin decoherence dynamics of Er$^{3+}$ in CeO$_2$ film

Developing telecom-compatible spin-photon interfaces is essential towards scalable quantum networks. Erbium ions (Er$^{3+}$) exhibit a unique combination of a telecom (1.5 $\mu$m) optical transition and an effective spin-$1/2$ ground state, but identifying a host that enables heterogeneous device integration while preserving long optical and spin coherence remains an open challenge. We explore a new platform of Er$^{3+}$:CeO$_2$ films on silicon, offering low nuclear spin density and the potential for on-chip integration. We demonstrate a 38.8 $\mu$s spin coherence, which can be extended to 176.4\nobreakspace $\mu$s with dynamical decoupling. Pairing experiments with cluster correlation expansion calculations, we identify spectral diffusion-induced Er$^{3+}$ spin flips as the dominant decoherence mechanism and provide pathways to millisecond-scale coherence.

quant-ph↗

arXiv2025

Towards dislocation-driven quantum interconnects

A central problem in the deployment of quantum technologies is the realization of robust architectures for quantum interconnects. We propose to engineer interconnects in semiconductors and insulators by patterning spin qubits at dislocations, thus forming quasi one-dimensional lines of entangled point defects. To gain insight into the feasibility and control of dislocation-driven interconnects, we investigate the optical cycle and coherence properties of nitrogen-vacancy (NV) centers in diamond, in proximity of dislocations, using a combination of advanced first-principles calculations. We show that one can engineer spin defects with properties similar to those of their bulk counterparts, including charge stability and a favorable optical cycle, and that NV centers close to dislocations have much improved coherence properties. Finally, we predict optically detected magnetic resonance spectra that may facilitate the experimental identification of specific defect configurations. Our results provide a theoretical foundation for the engineering of one-dimensional arrays of spin defects in the solid state.

cond-mat.mtrl-sci↗

arXiv2025

Probing aqueous interfaces with spin defects

Understanding the physical and chemical properties of aqueous interfaces is important in diverse fields of science, ranging from biology and chemistry to materials science. In spite of crucial progress in surface sensitive spectroscopic techniques over the past decades, the microscopic properties of aqueous interfaces remain difficult to measure. Here we explore the use of noise spectroscopy to characterize interfacial properties, specifically of quantum sensors hosted in two-dimensional materials in contact with water. We combine molecular dynamics simulations of water/graphene interfaces and the calculations of the spin dynamics of an NV-like color center, and we investigate the impact of interfacial water and simple ions on the decoherence time of the defect. We show that the Hahn echo coherence time of the NV center is sensitive to motional narrowing and to the hydrogen bonding arrangement and the dynamical properties of water and ions at the interface. We present results as a function of the liquid temperature, strength of the water-surface interaction, and for varied mono-valent and di-valent ions, highlighting the broad applicability of near-surface qubits to gain insight into the properties of aqueous interfaces.

physics.chem-ph↗

arXiv2025

High-throughput spin-bath characterization of spin-defects in semiconductors

Detailed knowledge of the local environments of spin-defects in semiconductors, such as nitrogen vacancy (NV) centers in diamond or divacancies in silicon carbide, is crucial for optimizing control and entanglement protocols in quantum sensing and information applications. However, a direct experimental characterization of individual defect environments is not scalable, as spin bath measurements are extremely time consuming. In this work, we address the ill-posed inverse problem of recovering the atomic positions and hyperfine couplings of random nuclei surrounding spin-defects from sparse experimental coherence signals, which can be obtained in hours. To address the challenge to determine the number of isotopic nuclear spins along with their hyperfine couplings, we employ a trans-dimensional Bayesian approach that incorporates ab initio data. This approach provides posterior distributions of the numbers, hyperfine couplings, and locations of nuclear spins present in the sample. In addition to enabling high-throughput screening of spin-defects, we demonstrate how this trans-dimensional Bayesian approach can guide experimental design for dynamical decoupling experiments to detect nuclear spins within targeted hyperfine coupling regimes. While the primary focus is on accelerating spin-defect characterization, this Bayesian approach also lays the foundation for digital twin studies of spin-defects, where a virtual model of the spin-defect system evolves in real time with ongoing experimental measurements. Together, the set of tools we designed and applied paves the way for scalable deployment of spin-defects in semiconductors for quantum sensing and information applications.

quant-ph↗