Polaron pattern recognition
in correlated oxide surfaces

@article{Ryan_2024a,

title = {Quantitative Measurement of Cooperative Binding in Partially Dissociated Water Dimers at the Hematite “R-Cut” Surface},

author = {Paul T. P. Ryan and Panukorn Sombut and Ali Rafsanjani-Abbasi and Chunlei Wang and Fulden Eratam and Francesco Goto and Ulrike Diebold and Matthias Meier and David A. Duncan and Gareth S. Parkinson},

url = {https://arxiv.org/abs/2406.18264

https://pubs.acs.org/doi/10.1021/acs.jpcc.4c04537},

year  = {2024},

date = {2024-09-30},

urldate = {2024-06-26},

journal = {The Journal of Physical Chemistry C},

abstract = {Water–solid interfaces pervade the natural environment and modern technology. On some surfaces, water–water interactions induce the formation of partially dissociated interfacial layers; understanding why is important to model processes in catalysis or mineralogy. The complexity of the partially dissociated structures often makes it difficult to probe them quantitatively. Here, we utilize normal incidence X-ray standing waves (NIXSW) to study the structure of partially dissociated water dimers (H_{2}O–OH) at the α-Fe_{2}O_{3}(012) surface (also called the (11̅02) or “R-cut” surface): a system simple enough to be tractable yet complex enough to capture the essential physics. We find the H_{2}O and terminal OH groups to be the same height above the surface within experimental error (1.45 ± 0.04 and 1.47 ± 0.02 Å, respectively), in line with DFT-based calculations that predict comparable Fe–O bond lengths for both water and OH species. This result is understood in the context of cooperative binding, where the formation of the H-bond between adsorbed H_{2}O and OH induces the H_{2}O to bind more strongly and the OH to bind more weakly compared to when these species are isolated on the surface. The surface OH formed by the liberated proton is found to be in plane with a bulk truncated (012) surface (−0.01 ± 0.02 Å). DFT calculations based on various functionals correctly model the cooperative effect but overestimate the water–surface interaction.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Redondo2024,

title = {Real-space investigation of polarons in hematite Fe2O3},

author = {Jesus Redondo and Michele Reticcioli and Vit Gabriel and Dominik Wrana and Florian Ellinger and Michele Riva and Giada Franceschi and Erik Rheinfrank and Igor Sokolovic and Zdenek Jakub and Florian Kraushofer and Aji Alexander and Laerte L. Patera and Jascha Repp and Michael Schmid and Ulrike Diebold and Gareth S. Parkinson and Cesare Franchini and Pavel Kocan and Martin Setvin},

url = {https://arxiv.org/abs/2303.17945},

year  = {2024},

date = {2024-09-27},

urldate = {2023-03-31},

journal = {Science Advances},

abstract = {In polarizable materials, electronic charge carriers interact with the surrounding ions, leading to quasiparticle behaviour. The resulting polarons play a central role in many materials properties including electrical transport, optical properties, surface reactivity and magnetoresistance, and polaron properties are typically investigated indirectly through such macroscopic characteristics. Here, noncontact atomic force microscopy (nc-AFM) is used to directly image polarons in Fe_{2}O_{3} at the single quasiparticle limit. A combination of Kelvin probe force microscopy (KPFM) and kinetic Monte Carlo (KMC) simulations shows that Ti doping dramatically enhances the mobility of electron polarons, and density functional theory (DFT) calculations indicate that a metallic transition state is responsible for the enhancement. In contrast, hole polarons are significantly less mobile and their hopping is hampered further by the introduction of trapping centres.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Birschitzky_2024b,

title = {Machine Learning Small Polaron Dynamics},

author = {Viktor C. Birschitzky and Luca Leoni and Michele Reticcioli and Cesare Franchini},

url = {https://arxiv.org/abs/2409.16179},

year  = {2024},

date = {2024-09-24},

journal = {arXiv},

abstract = {Polarons are crucial for charge transport in semiconductors, significantly impacting material properties and device performance. The dynamics of small polarons can be investigated using first-principles molecular dynamics. However, the limited timescale of these simulations presents a challenge for adequately sampling infrequent polaron hopping events. Here, we introduce a message-passing neural network that learns the polaronic potential energy surface by encoding the polaronic state, allowing for simulations of polaron hopping dynamics at the nanosecond scale. By leveraging the statistical significance of the long timescale, our framework can accurately estimate polaron (anisotropic) mobilities and activation barriers in prototypical polaronic oxides across different scenarios (hole polarons in rocksalt MgO and electron polarons in pristine and F-doped rutile TiO_{2}) in excellent agreement with experimental observations.},

keywords = {P07},

pubstate = {published},

tppubtype = {article}

}

@article{Rafsanjani_2024a,

title = {Digging Its Own Site: Linear Coordination Stabilizes a Pt_{1}/Fe_{2}O_{3} Single-Atom Catalyst},

author = {Ali Rafsanjani-Abbasi and Florian Buchner and Faith J. Lewis and Lena Puntscher and Florian Kraushofer and Panukorn Sombut and Moritz Eder and Jiří Pavelec and Erik Rheinfrank and Giada Franceschi and Viktor Birschitzky and Michele Riva and Cesare Franchini and Michael Schmid and Ulrike Diebold and Matthias Meier and Georg K. H. Madsen and Gareth S. Parkinson},

url = {https://doi.org/10.1021/acsnano.4c08781},

year  = {2024},

date = {2024-09-18},

urldate = {2024-09-18},

journal = {ACS Nano},

abstract = {Determining the local coordination of the active site is a prerequisite for the reliable modeling of single-atom catalysts (SACs). Obtaining such information is difficult on powder-based systems and much emphasis is placed on density functional theory computations based on idealized low-index surfaces of the support. In this work, we investigate how Pt atoms bind to the (11̅02) facet of α-Fe_{2}O_{3}; a common support material in SACs. Using a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and an extensive computational evolutionary search, we find that Pt atoms significantly reconfigure the support lattice to facilitate a pseudolinear coordination to surface oxygen atoms. Despite breaking three surface Fe–O bonds, this geometry is favored by 0.84 eV over the best configuration involving an unperturbed support. We suggest that the linear O–Pt–O configuration is common in reactive Pt-based SAC systems because it balances thermal stability with the ability to adsorb reactants from the gas phase. Moreover, we conclude that extensive structural searches are necessary to determine realistic active site geometries in single-atom catalysis.},

keywords = {P02, P04, P07, P09},

pubstate = {published},

tppubtype = {article}

}

@article{Wang_2024b,

title = {A Multitechnique Study of C_{2}H_{4} Adsorption on a Model Single-Atom Rh_{1} Catalyst},

author = {Chunlei Wang and Panukorn Sombut and Lena Puntscher and Manuel Ulreich and Jiri Pavelec and David Rath and Jan Balajka and Matthias Meier and Michael Schmid and Ulrike Diebold and Cesare Franchini and Gareth S. Parkinson},

url = {https://doi.org/10.1021/acs.jpcc.4c03588},

year  = {2024},

date = {2024-09-05},

journal = {The Journal of Physical Chemistry C},

volume = {128},

issue = {37},

pages = {15404–15411},

abstract = {Single-atom catalysts are potentially ideal model systems to investigate structure–function relationships in catalysis if the active sites can be uniquely determined. In this work, we study the interaction of C_{2}H_{4} with a model Rh/Fe_{3}O_{4}(001) catalyst that features 2-, 5-, and 6-fold coordinated Rh adatoms, as well as Rh clusters. Using multiple surface-sensitive techniques in combination with calculations of density functional theory (DFT), we follow the thermal evolution of the system and disentangle the behavior of the different species. C_{2}H_{4} adsorption is strongest at the 2-fold coordinated Rh_{1} with a DFT-determined adsorption energy of −2.26 eV. However, desorption occurs at lower temperatures than expected because the Rh migrates into substitutional sites within the support, where the molecule is more weakly bound. The adsorption energy at the 5-fold coordinated Rh sites is predicated to be −1.49 eV, but the superposition of this signal with that from small Rh clusters and additional heterogeneity leads to a broad C_{2}H_{4} desorption shoulder in TPD above room temperature.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Tresca2024,

title = {Evidence of Molecular Hydrogen in the N-doped LuH_{3} System: a Possible Path to Superconductivity?},

author = {Cesare Tresca and Pietro Maria Forcella and Andrea Angeletti and Luigi Ranalli and Cesare Franchini and Michele Reticcioli and Gianni Profeta},

url = {https://arxiv.org/abs/2308.03619

https://doi.org/10.1038/s41467-024-51348-z},

year  = {2024},

date = {2024-08-23},

urldate = {2023-08-07},

journal = {Nature Communications},

volume = {15},

pages = {7283},

abstract = {The discovery of ambient superconductivity would mark an epochal breakthrough long-awaited for over a century, potentially ushering in unprecedented scientific and technological advancements. The recent findings on high-temperature superconducting phases in various hydrides under high pressure have ignited optimism, suggesting that the realization of near-ambient superconductivity might be on the horizon. However, the preparation of hydride samples tends to promote the emergence of various metastable phases, marked by a low level of experimental reproducibility. Identifying these phases through theoretical and computational methods entails formidable challenges, often resulting in controversial outcomes. In this paper, we consider N-doped LuH_{3} as a prototypical complex hydride: By means of machine-learning-accelerated force-field molecular dynamics, we have identified the formation of H_{2} molecules stabilized at ambient pressure by nitrogen impurities. Importantly, we demonstrate that this molecular phase plays a pivotal role in the emergence of a dynamically stable, low-temperature, experimental-ambient-pressure superconductivity. The potential to stabilize hydrogen in molecular form through chemical doping opens up a novel avenue for investigating disordered phases in hydrides and their transport properties under near-ambient conditions.},

keywords = {P07},

pubstate = {published},

tppubtype = {article}

}

@article{Romano_2024a,

title = {Structure and dynamics of the magnetite(001)/water interface from molecular dynamics simulations based on a neural network potential},

author = {Salvatore Romano and Pablo Montero de Hijes and Matthias Meier and Georg Kresse and Cesare Franchini and Christoph Dellago},

url = {https://arxiv.org/abs/2408.11538},

year  = {2024},

date = {2024-08-21},

urldate = {2024-08-21},

journal = {arXiv},

abstract = {The magnetite/water interface is commonly found in nature and plays a crucial role in various technological applications. However, our understanding of its structural and dynamical properties at the molecular scale remains still limited. In this study, we develop an efficient Behler-Parrinello neural network potential (NNP) for the magnetite/water system, paying particular attention to the accurate generation of reference data with density functional theory. Using this NNP, we performed extensive molecular dynamics simulations of the magnetite (001) surface across a wide range of water coverages, from the single molecule to bulk water. Our simulations revealed several new ground states of low coverage water on the Subsurface Cation Vacancy (SCV) model and yielded a density profile of water at the surface that exhibits marked layering. By calculating mean square displacements, we obtained quantitative information on the diffusion of water molecules on the SCV for different coverages, revealing significant anis},

keywords = {P03, P07, P12},

pubstate = {published},

tppubtype = {article}

}

@article{PhysRevResearch.6.033041,

title = {Global sampling of Feynman's diagrams through normalizing flow},

author = {Luca Leoni and Cesare Franchini},

url = {https://link.aps.org/doi/10.1103/PhysRevResearch.6.033041},

doi = {10.1103/PhysRevResearch.6.033041},

year  = {2024},

date = {2024-07-08},

journal = {Physical Review Research},

volume = {6},

issue = {3},

pages = {033041},

abstract = {Normalizing flows (NF) are powerful generative models with increasing applications in augmenting Monte Carlo algorithms due to their high flexibility and expressiveness. In this work we explore the integration of NF in the diagrammatic Monte Carlo (DMC) method, presenting an architecture designed to sample the intricate multidimensional space of Feynman's diagrams through dimensionality reduction. By decoupling the sampling of diagram order and interaction times, the flow focuses on one interaction at a time. This enables one to construct a general diagram by employing the same unsupervised model iteratively, dressing a zero-order diagram with interactions determined by the previously sampled order. The resulting NF-augmented DMC method is tested on the widely used single-site Holstein polaron model in the entire electron-phonon coupling regime. The obtained data show that the model accurately reproduces the diagram distribution by reducing sample correlation and observables' statistical error, constituting the first example of global sampling strategy for connected Feynman's diagrams in the DMC method},

keywords = {P07},

pubstate = {published},

tppubtype = {article}

}

@article{Birschitzky_2024a,

title = {Machine learning-based prediction of polaron-vacancy patterns on the TiO_{2}(110) surface},

author = {Viktor Birschitzky and Igor Sokolovic and Michael Prezzi and Krisztian Palotas and Martin Setvin and Ulrike Diebold and Michele Reticcioli and Cesare Franchini},

url = {https://www.nature.com/articles/s41524-024-01289-4},

doi = {https://doi.org/10.1038/s41524-024-01289-4},

year  = {2024},

date = {2024-05-06},

urldate = {2024-05-06},

journal = {npj Computational Materials},

volume = {10},

number = {89},

abstract = {The multifaceted physics of oxides is shaped by their composition and the presence of defects, which are often accompanied by the formation of polarons. The simultaneous presence of polarons and defects, and their complex interactions, pose challenges for first-principles simulations and experimental techniques. In this study, we leverage machine learning and a first-principles database to analyze the distribution of surface oxygen vacancies (V_{O}) and induced small polarons on rutile TiO_{2}(110), effectively disentangling the interactions between polarons and defects. By combining neural-network supervised learning and simulated annealing, we elucidate the inhomogeneous VO distribution observed in scanning probe microscopy (SPM). Our approach allows us to understand and predict defective surface patterns at enhanced length scales, identifying the specific role of individual types of defects. Specifically, surface-polaron-stabilizing V_{O}-configurations are identified, which could have consequences for surface reactivity.},

keywords = {P02, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Celiberti2024,

title = {Spin-orbital Jahn-Teller bipolarons},

author = {Lorenzo Celiberti and Dario Fiore Mosca and Giuseppe Allodi and Leonid V. Pourovskii and Anna Tassetti and Paola Caterina Forino and Rong Cong and Erick Garcia and Phuong M. Tran and Roberto De Renzi and Patrick M. Woodward and Vesna F. Mitrović and Samuele Sanna and Cesare Franchini},

url = {https://doi.org/10.1038/s41467-024-46621-0},

doi = {10.1038/s41467-024-46621-0},

year  = {2024},

date = {2024-03-18},

urldate = {2024-03-18},

journal = {Nature Communications},

volume = {15},

number = {2429},

abstract = {Polarons and spin-orbit (SO) coupling are distinct quantum effects that play a critical role in charge transport and spin-orbitronics. Polarons originate from strong electron-phonon interaction and are ubiquitous in polarizable materials featuring electron localization, in particular 3d transition metal oxides (TMOs). On the other hand, the relativistic coupling between the spin and orbital angular momentum is notable in lattices with heavy atoms and develops in 5d TMOs, where electrons are spatially delocalized. Here we combine ab initio calculations and magnetic measurements to show that these two seemingly mutually exclusive interactions are entangled in the electron-doped SO-coupled Mott insulator Ba_{2}Na_{1−x}Ca_{x}OsO_{6} (0 < x < 1), unveiling the formation of spin-orbital bipolarons. Polaron charge trapping, favoured by the Jahn-Teller lattice activity, converts the Os 5d^{1} spin-orbital J_{eff} = 3/2 levels, characteristic of the parent compound Ba_{2}NaOsO_{6} (BNOO), into a bipolaron 5d^{2} J_{eff} = 2 manifold, leading to the coexistence of different J-effective states in a single-phase material. The gradual increase of bipolarons with increasing doping creates robust in-gap states that prevents the transition to a metal phase even at ultrahigh doping, thus preserving the Mott gap across the entire doping range from d^{1} BNOO to d^{2} Ba_{2}CaOsO_{6} (BCOO).},

keywords = {P07},

pubstate = {published},

tppubtype = {article}

}