Matteo Cococcioni
Current Organizations / Institutes
The organizations/institutes from the scholar's latest article
Research Subjects
Research Interests
Matteo Cococcioni has a total of 67 co-authors. Here are the top co-authors by number of shared publications:
- Iurii Timrov
PSI Center for Scientific Computing, Theory and Data Paul Scherrer Institute 5232 Villigen PSI Switzerland
6 shared publications - Andrea Floris
University of Lincoln Brayford Pool
5 shared publications - Nicola Marzari
Paul Scherrer Institute
4 shared publications - Ismaila Dabo
Department of Materials Science and Engineering, Carnegie Mellon University 3 , 5000 Forbes Avenue, Pittsburgh, Pennsylvania 15213
2 shared publications - Mohammed Mohsin Khan
Department of Materials Science and Engineering, and Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
2 shared publications - Nicole E. Kirchner-Hall
Department of Materials Science and Engineering, and Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
2 shared publications
Latest Publications
- Open Access
- 13 April 2026
- Published by Royal Society of Chemistry (RSC) in Nanoscale
- Vol. 18 (19) , 9994-10011
Spin–orbit coupling and beyond in chiral-induced spin selectivity
Schematic illustration of the chiral-induced spin selectrivity effect. An unpolarized current acquires a finite spin polarisation by flowing through a chiral molecule whose geometrical chirality imbalances the two spins' transmission rates. Graphical abstract image refined using Microsoft Copilot.
- 13 April 2026
- Published by Royal Society of Chemistry (RSC) in Nanoscale
- Vol. 18 (19) , 9994-10011
Open AccessSpin–orbit coupling and beyond in chiral-induced spin selectivity
Schematic illustration of the chiral-induced spin selectrivity effect. An unpolarized current acquires a finite spin polarisation by flowing through a chiral molecule whose geometrical chirality imbalances the two spins' transmission rates. Graphical abstract image refined using Microsoft Copilot.
- 2 June 2025
- Published by American Physical Society (APS) in Physical Review B
- Vol. 111 (21)
Magnetic properties of and molecular rings from ab initio calculations- 2 June 2025
- Published by American Physical Society (APS) in Physical Review B
- Vol. 111 (21)
Magnetic properties of and molecular rings from ab initio calculations- Open Access
- 13 February 2024
- Published by American Physical Society (APS) in PRX Energy
- Vol. 3 (1) , 013007
Ternary Oxides of - and -Block Metals for Photocatalytic Solar-to-Hydrogen ConversionOxides containing metals or metalloids from the block of the periodic table (e.g., , , , , and ) are of technological interest as transparent conductors and light absorbers for solar-energy conversion due to the tunability of their electronic conductivity and optical absorption. Comparatively, these oxides have found limited applications in hydrogen photoelectrolysis, primarily due to their high electronegativity, which impedes electron transfer for reducing protons into hydrogen. We have shown recently that inserting -block cations into -block metal oxides is effective at lowering electronegativities while affording further control of band gaps. Here, we explain the origins of this dual tunability by demonstrating the mediator role of -block cations in modulating orbital hybridization while not contributing to frontier electronic states. From this result, we carry out a comprehensive computational study of 109 ternary oxides of - and -block metal elements as candidate photocatalysts for solar hydrogen generation. We down-select the most desirable materials using band gaps and band edges obtained from Hubbard-corrected density-functional theory, with Hubbard parameters computed entirely from first principles, evaluate the stability of these oxides in aqueous conditions, and characterize experimentally four of the remaining materials, synthesized with high phase uniformity, to validate and further develop the computational models. We thus propose nine oxide semiconductors, including , , and , which, to the extent of our literature review, have not been previously considered as water-splitting photocatalysts.- 13 February 2024
- Published by American Physical Society (APS) in PRX Energy
- Vol. 3 (1) , 013007
Open AccessTernary Oxides of - and -Block Metals for Photocatalytic Solar-to-Hydrogen ConversionOxides containing metals or metalloids from the block of the periodic table (e.g., , , , , and ) are of technological interest as transparent conductors and light absorbers for solar-energy conversion due to the tunability of their electronic conductivity and optical absorption. Comparatively, these oxides have found limited applications in hydrogen photoelectrolysis, primarily due to their high electronegativity, which impedes electron transfer for reducing protons into hydrogen. We have shown recently that inserting -block cations into -block metal oxides is effective at lowering electronegativities while affording further control of band gaps. Here, we explain the origins of this dual tunability by demonstrating the mediator role of -block cations in modulating orbital hybridization while not contributing to frontier electronic states. From this result, we carry out a comprehensive computational study of 109 ternary oxides of - and -block metal elements as candidate photocatalysts for solar hydrogen generation. We down-select the most desirable materials using band gaps and band edges obtained from Hubbard-corrected density-functional theory, with Hubbard parameters computed entirely from first principles, evaluate the stability of these oxides in aqueous conditions, and characterize experimentally four of the remaining materials, synthesized with high phase uniformity, to validate and further develop the computational models. We thus propose nine oxide semiconductors, including , , and , which, to the extent of our literature review, have not been previously considered as water-splitting photocatalysts. - Open Access
Accurate electronic properties and intercalation voltages of olivine-type Li-ion cathode materials from extended Hubbard functionals
The design of novel cathode materials for Li-ion batteries would greatly benefit from accurate first-principles predictions of structural, electronic, and magnetic properties as well as intercalation voltages in compounds containing transition-metal elements. For such systems, density-functional theory (DFT) with standard (semi-)local exchange-correlation functionals is of limited use as it often fails due to strong self-interaction errors that are especially relevant in the partially filled $d$ shells. Here, we perform a detailed comparative study of the phospho-olivine cathode materials Li$_x$MnPO$_4$, Li$_x$FePO$_4$, and the mixed transition metal Li$_x$Mn$_{1/2}$Fe$_{1/2}$PO$_4$ ($x=0, 1/4, 1/2, 3/4, 1$) using four electronic-structure methods: DFT, DFT+$U$, DFT+$U$+$V$, and HSE06. We show that DFT+$U$+$V$, with onsite $U$ and intersite $V$ Hubbard parameters determined from first principles and self-consistently with respect to the structural parameters by means of density-functional perturbation theory (linear response), provides the most accurate description of the electronic structure of these challenging compounds. In particular, we demonstrate that DFT+$U$+$V$ displays very clearly "digital" changes in oxidation states of the transition-metal ions in all compounds, including the mixed-valence phases occurring at intermediate Li concentrations, leading to voltages in remarkable agreement with experiments. We show that the inclusion of intersite Hubbard interactions is essential for the accurate prediction of thermodynamic quantities, balancing the drive for localization induced by the onsite $U$ with intersite $V$ orbital hybridizations.Open AccessAccurate electronic properties and intercalation voltages of olivine-type Li-ion cathode materials from extended Hubbard functionals
The design of novel cathode materials for Li-ion batteries would greatly benefit from accurate first-principles predictions of structural, electronic, and magnetic properties as well as intercalation voltages in compounds containing transition-metal elements. For such systems, density-functional theory (DFT) with standard (semi-)local exchange-correlation functionals is of limited use as it often fails due to strong self-interaction errors that are especially relevant in the partially filled $d$ shells. Here, we perform a detailed comparative study of the phospho-olivine cathode materials Li$_x$MnPO$_4$, Li$_x$FePO$_4$, and the mixed transition metal Li$_x$Mn$_{1/2}$Fe$_{1/2}$PO$_4$ ($x=0, 1/4, 1/2, 3/4, 1$) using four electronic-structure methods: DFT, DFT+$U$, DFT+$U$+$V$, and HSE06. We show that DFT+$U$+$V$, with onsite $U$ and intersite $V$ Hubbard parameters determined from first principles and self-consistently with respect to the structural parameters by means of density-functional perturbation theory (linear response), provides the most accurate description of the electronic structure of these challenging compounds. In particular, we demonstrate that DFT+$U$+$V$ displays very clearly "digital" changes in oxidation states of the transition-metal ions in all compounds, including the mixed-valence phases occurring at intermediate Li concentrations, leading to voltages in remarkable agreement with experiments. We show that the inclusion of intersite Hubbard interactions is essential for the accurate prediction of thermodynamic quantities, balancing the drive for localization induced by the onsite $U$ with intersite $V$ orbital hybridizations. - Open Access
- 31 October 2022
- Published by American Physical Society (APS) in PRX Energy
- Vol. 1 (3) , 033003
Accurate Electronic Properties and Intercalation Voltages of Olivine-Type Li-Ion Cathode Materials from Extended Hubbard Functionals
The design of novel cathode materials for -ion batteries would greatly benefit from accurate first-principles predictions of structural, electronic, and magnetic properties as well as intercalation voltages in compounds containing transition-metal elements. For such systems, density-functional theory (DFT) with standard (semi)local exchange-correlation functionals is of limited use as it often fails due to strong self-interaction errors that are especially relevant in the partially filled shells. Here, we perform a detailed comparative study of the phospho-olivine cathode materials , and the mixed transition metal () using four electronic-structure methods: DFT, DFT+, DFT++, and HSE06. We show that DFT++, with onsite and intersite Hubbard parameters determined from first principles and self-consistently with respect to the structural parameters by means of density-functional perturbation theory (linear response), provides the most accurate description of the electronic structure of these challenging compounds. In particular, we demonstrate that DFT++ displays very clearly “digital” changes in oxidation states of the transition-metal ions in all compounds, including the mixed-valence phases occurring at intermediate concentrations, leading to voltages in remarkable agreement with experiments. We show that the inclusion of intersite Hubbard interactions is essential for the accurate prediction of thermodynamic quantities, balancing the drive for localization induced by the onsite with intersite orbital hybridizations. At variance with other methods, DFT++ describes accurately such localization-hybridization interplay, and thus opens the door for the study of more complex cathode materials as well as for a reliable exploration of the chemical space of compounds for -ion batteries.- 31 October 2022
- Published by American Physical Society (APS) in PRX Energy
- Vol. 1 (3) , 033003
Open AccessAccurate Electronic Properties and Intercalation Voltages of Olivine-Type Li-Ion Cathode Materials from Extended Hubbard Functionals
The design of novel cathode materials for -ion batteries would greatly benefit from accurate first-principles predictions of structural, electronic, and magnetic properties as well as intercalation voltages in compounds containing transition-metal elements. For such systems, density-functional theory (DFT) with standard (semi)local exchange-correlation functionals is of limited use as it often fails due to strong self-interaction errors that are especially relevant in the partially filled shells. Here, we perform a detailed comparative study of the phospho-olivine cathode materials , and the mixed transition metal () using four electronic-structure methods: DFT, DFT+, DFT++, and HSE06. We show that DFT++, with onsite and intersite Hubbard parameters determined from first principles and self-consistently with respect to the structural parameters by means of density-functional perturbation theory (linear response), provides the most accurate description of the electronic structure of these challenging compounds. In particular, we demonstrate that DFT++ displays very clearly “digital” changes in oxidation states of the transition-metal ions in all compounds, including the mixed-valence phases occurring at intermediate concentrations, leading to voltages in remarkable agreement with experiments. We show that the inclusion of intersite Hubbard interactions is essential for the accurate prediction of thermodynamic quantities, balancing the drive for localization induced by the onsite with intersite orbital hybridizations. At variance with other methods, DFT++ describes accurately such localization-hybridization interplay, and thus opens the door for the study of more complex cathode materials as well as for a reliable exploration of the chemical space of compounds for -ion batteries. - 21 December 2021
- Published by American Chemical Society (ACS) in ACS Applied Materials & Interfaces
- Vol. 14 (1) , 543-556
Energy Level Alignment at the Cobalt Phosphate/Electrolyte Interface: Intrinsic Stability vs Interfacial Chemical Reactions in 5 V Lithium Ion Batteries
The intrinsic stability of the 5 V LiCoPO4–LiCo2P3O10 thin-film (carbon-free) cathode material coated with MoO3 thin layer is studied using a comprehensive synchrotron electron spectroscopy in situ approach combined with first-principle calculations. The atomic–molecular level study demonstrates fully reversible electronic properties of the cathode after the first electrochemical cycle. The polyanionic oxide is not involved in chemical reactions with the fluoroethylene-containing liquid electrolyte even when charged to 5.1 V vs Li+/Li. The high stability of the cathode is explained on the basis of the developed energy level model. In contrast, the chemical composition of the cathode–electrolyte interface evolves continuously by involving MoO3 in the decomposition reaction with consequent leaching of oxide from the surface. The proposed mechanisms of chemical reactions are attributed to external electrolyte oxidation via charge transfer from the relevant electron level to the MoO3 valence band state and internal electrolyte oxidation via proton transfer to the solvents. This study provides a deeper insight into the development of both a doping strategy to enhance the electronic conductivity of high-voltage cathode materials and an efficient surface coating against unfavorable interfacial chemical reactions.
- 21 December 2021
- Published by American Chemical Society (ACS) in ACS Applied Materials & Interfaces
- Vol. 14 (1) , 543-556
Energy Level Alignment at the Cobalt Phosphate/Electrolyte Interface: Intrinsic Stability vs Interfacial Chemical Reactions in 5 V Lithium Ion Batteries
The intrinsic stability of the 5 V LiCoPO4–LiCo2P3O10 thin-film (carbon-free) cathode material coated with MoO3 thin layer is studied using a comprehensive synchrotron electron spectroscopy in situ approach combined with first-principle calculations. The atomic–molecular level study demonstrates fully reversible electronic properties of the cathode after the first electrochemical cycle. The polyanionic oxide is not involved in chemical reactions with the fluoroethylene-containing liquid electrolyte even when charged to 5.1 V vs Li+/Li. The high stability of the cathode is explained on the basis of the developed energy level model. In contrast, the chemical composition of the cathode–electrolyte interface evolves continuously by involving MoO3 in the decomposition reaction with consequent leaching of oxide from the surface. The proposed mechanisms of chemical reactions are attributed to external electrolyte oxidation via charge transfer from the relevant electron level to the MoO3 valence band state and internal electrolyte oxidation via proton transfer to the solvents. This study provides a deeper insight into the development of both a doping strategy to enhance the electronic conductivity of high-voltage cathode materials and an efficient surface coating against unfavorable interfacial chemical reactions.
- 16 September 2021
- Published by American Physical Society (APS) in Physical Review Letters
- Vol. 127 (12) , 126404
Ab Initio Electron-Phonon Interactions in Correlated Electron Systems
Electron-phonon () interactions are pervasive in condensed matter, governing phenomena such as transport, superconductivity, charge-density waves, polarons, and metal-insulator transitions. First-principles approaches enable accurate calculations of interactions in a wide range of solids. However, they remain an open challenge in correlated electron systems (CES), where density functional theory often fails to describe the ground state. Therefore reliable calculations remain out of reach for many transition metal oxides, high-temperature superconductors, Mott insulators, planetary materials, and multiferroics. Here we show first-principles calculations of interactions in CES, using the framework of Hubbard-corrected density functional theory () and its linear response extension (), which can describe the electronic structure and lattice dynamics of many CES. We showcase the accuracy of this approach for a prototypical Mott system, CoO, carrying out a detailed investigation of its interactions and electron spectral functions. While standard DFPT gives unphysically divergent and short-ranged interactions, is shown to remove the divergences and properly account for the long-range Fröhlich interaction, allowing us to model polaron effects in a Mott insulator. Our work establishes a broadly applicable and affordable approach for quantitative studies of interactions in CES, a novel theoretical tool to interpret experiments in this broad class of materials.- 16 September 2021
- Published by American Physical Society (APS) in Physical Review Letters
- Vol. 127 (12) , 126404
Ab Initio Electron-Phonon Interactions in Correlated Electron Systems
Electron-phonon () interactions are pervasive in condensed matter, governing phenomena such as transport, superconductivity, charge-density waves, polarons, and metal-insulator transitions. First-principles approaches enable accurate calculations of interactions in a wide range of solids. However, they remain an open challenge in correlated electron systems (CES), where density functional theory often fails to describe the ground state. Therefore reliable calculations remain out of reach for many transition metal oxides, high-temperature superconductors, Mott insulators, planetary materials, and multiferroics. Here we show first-principles calculations of interactions in CES, using the framework of Hubbard-corrected density functional theory () and its linear response extension (), which can describe the electronic structure and lattice dynamics of many CES. We showcase the accuracy of this approach for a prototypical Mott system, CoO, carrying out a detailed investigation of its interactions and electron spectral functions. While standard DFPT gives unphysically divergent and short-ranged interactions, is shown to remove the divergences and properly account for the long-range Fröhlich interaction, allowing us to model polaron effects in a Mott insulator. Our work establishes a broadly applicable and affordable approach for quantitative studies of interactions in CES, a novel theoretical tool to interpret experiments in this broad class of materials.- Open Access
The Different Story of π Bonds
We revisit “classical” issues in multiply bonded systems between main groups elements, namely the structural distortions that may occur at the multiple bonds and that lead, e.g., to trans-bent and bond-length alternated structures. The focus is on the role that orbital hybridization and electron correlation play in this context, here analyzed with the help of simple models for - and -bonds, numerically exact solutions of Hubbard Hamiltonians and first principles (density functional theory) investigations of an extended set of systems.Open AccessThe Different Story of π Bonds
We revisit “classical” issues in multiply bonded systems between main groups elements, namely the structural distortions that may occur at the multiple bonds and that lead, e.g., to trans-bent and bond-length alternated structures. The focus is on the role that orbital hybridization and electron correlation play in this context, here analyzed with the help of simple models for - and -bonds, numerically exact solutions of Hubbard Hamiltonians and first principles (density functional theory) investigations of an extended set of systems. - Open Access
- 23 April 2021
- Published by MDPI AG in Applied Sciences
- Vol. 11 (9) , 3806
Magnetic Energy Landscape of Dimolybdenum Tetraacetate on a Bulk Insulator Surface
The magnetic states and the magnetic anisotropy barrier of a transition metal molecular complex, dimolybdenum tetraacetate, are investigated via density functional theory (DFT). Calculations are performed in the gas phase and on a calcite (10.4) bulk insulating surface, using the Generalized-Gradient Approximation (GGA)-PBE and the Hubbard-corrected DFT + U and DFT + U + V functionals. The molecular complex (denoted MoMo) contains two central metallic molybdenum atoms, embedded in a square cage of acetate groups. Recently, MoMo was observed to form locally regular networks of immobile molecules on calcite (10.4), at room conditions. As this is the first example of a metal-coordinated molecule strongly anchored to an insulator surface at room temperature, we explore here its magnetic properties with the aim to understand whether the system could be assigned features of a single molecule magnet (SMM) and could represent the basis to realize stable magnetic networks on insulators. After an introductory review on SMMs, we show that, while the uncorrected GGA-PBE functional stabilizes MoMo in a nonmagnetic state, the DFT + U and DFT + U + V approaches stabilize an antiferromagnetic ground state and several meta-stable ferromagnetic and ferrimagnetic states. Importantly, the energy landscape of magnetic states remains almost unaltered on the insulating surface. Finally, via a noncollinear magnetic formalism and a newly introduced algorithm, we calculate the magnetic anisotropy barrier, whose value indicates the stability of the molecule’s magnetic moment.
- 23 April 2021
- Published by MDPI AG in Applied Sciences
- Vol. 11 (9) , 3806
Open AccessMagnetic Energy Landscape of Dimolybdenum Tetraacetate on a Bulk Insulator Surface
The magnetic states and the magnetic anisotropy barrier of a transition metal molecular complex, dimolybdenum tetraacetate, are investigated via density functional theory (DFT). Calculations are performed in the gas phase and on a calcite (10.4) bulk insulating surface, using the Generalized-Gradient Approximation (GGA)-PBE and the Hubbard-corrected DFT + U and DFT + U + V functionals. The molecular complex (denoted MoMo) contains two central metallic molybdenum atoms, embedded in a square cage of acetate groups. Recently, MoMo was observed to form locally regular networks of immobile molecules on calcite (10.4), at room conditions. As this is the first example of a metal-coordinated molecule strongly anchored to an insulator surface at room temperature, we explore here its magnetic properties with the aim to understand whether the system could be assigned features of a single molecule magnet (SMM) and could represent the basis to realize stable magnetic networks on insulators. After an introductory review on SMMs, we show that, while the uncorrected GGA-PBE functional stabilizes MoMo in a nonmagnetic state, the DFT + U and DFT + U + V approaches stabilize an antiferromagnetic ground state and several meta-stable ferromagnetic and ferrimagnetic states. Importantly, the energy landscape of magnetic states remains almost unaltered on the insulating surface. Finally, via a noncollinear magnetic formalism and a newly introduced algorithm, we calculate the magnetic anisotropy barrier, whose value indicates the stability of the molecule’s magnetic moment.
- 11 March 2021
- Published by Royal Society of Chemistry (RSC) in Energy & Environmental Science
- Vol. 14 (4) , 2335-2348
Optimizing accuracy and efficacy in data-driven materials discovery for the solar production of hydrogen
The production of hydrogen fuels, via water splitting, is of practical relevance for meeting global energy needs and mitigating the environmental consequences of fossil-fuel-based transportation. Water photoelectrolysis has been proposed as a viable approach for generating hydrogen, provided that stable and inexpensive photocatalysts with conversion efficiencies over 10% can be discovered, synthesized at scale, and successfully deployed (Pinaud et al., Energy Environ. Sci., 2013, 6, 1983). While a number of first-principles studies have focused on the data-driven discovery of photocatalysts, in the absence of systematic experimental validation, the success rate of these predictions may be limited. We address this problem by developing a screening procedure with co-validation between experiment and theory to expedite the synthesis, characterization, and testing of the computationally predicted, most desirable materials. Starting with 70 150 compounds in the Materials Project database, the proposed protocol yielded 71 candidate photocatalysts, 11 of which were synthesized as single-phase materials. Experiments confirmed hydrogen generation and favorable band alignment for 6 of the 11 compounds, with the most promising ones belonging to the families of alkali and alkaline-earth indates and orthoplumbates. This study shows the accuracy of a nonempirical, Hubbard-corrected density-functional theory method to predict band gaps and band offsets at a fraction of the computational cost of hybrid functionals, and outlines an effective strategy to identify photocatalysts for solar hydrogen generation.
- 11 March 2021
- Published by Royal Society of Chemistry (RSC) in Energy & Environmental Science
- Vol. 14 (4) , 2335-2348
Optimizing accuracy and efficacy in data-driven materials discovery for the solar production of hydrogen
The production of hydrogen fuels, via water splitting, is of practical relevance for meeting global energy needs and mitigating the environmental consequences of fossil-fuel-based transportation. Water photoelectrolysis has been proposed as a viable approach for generating hydrogen, provided that stable and inexpensive photocatalysts with conversion efficiencies over 10% can be discovered, synthesized at scale, and successfully deployed (Pinaud et al., Energy Environ. Sci., 2013, 6, 1983). While a number of first-principles studies have focused on the data-driven discovery of photocatalysts, in the absence of systematic experimental validation, the success rate of these predictions may be limited. We address this problem by developing a screening procedure with co-validation between experiment and theory to expedite the synthesis, characterization, and testing of the computationally predicted, most desirable materials. Starting with 70 150 compounds in the Materials Project database, the proposed protocol yielded 71 candidate photocatalysts, 11 of which were synthesized as single-phase materials. Experiments confirmed hydrogen generation and favorable band alignment for 6 of the 11 compounds, with the most promising ones belonging to the families of alkali and alkaline-earth indates and orthoplumbates. This study shows the accuracy of a nonempirical, Hubbard-corrected density-functional theory method to predict band gaps and band offsets at a fraction of the computational cost of hybrid functionals, and outlines an effective strategy to identify photocatalysts for solar hydrogen generation.