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CaV₂O₄ cathode capacity is limited to about half theory at room temperature by a high-barrier ordered phase at half filling.

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2026-07-10 11:02 UTC pith:2OZQHQ5O

load-bearing objection Solid CE+GCMC+NEB study that cleanly ties the experimental half-capacity of CaV2O4 to a persistent γ+δ gap plus a ~1.16 eV barrier inside ordered γ; the central kinetic-limit claim holds. the 2 major comments →

arxiv 2607.08224 v1 pith:2OZQHQ5O submitted 2026-07-09 cond-mat.mtrl-sci

Phase stability and ionic transport in post-spinel CaV₂O₄ cathode

Dereje Bekele Tekliye , Javeed Ahmad Dar , Gopalakrishnan Sai Gautam This is my paper
classification cond-mat.mtrl-sci
keywords calcium-ion batteriespost-spinel CaV2O4phase diagramcluster expansionmigration barriersCa-vacancy orderingintercalation cathodes
verification ladder T0 review T1 audit T2 compute T3 formal T4 reserved

The pith

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

Post-spinel CaV₂O₄ looked promising as a calcium-battery cathode after computational screening, yet experiments only extract a fraction of the theoretical calcium. This work maps the full temperature–composition phase diagram of CaₓV₂O₄ and the calcium migration barriers in every accessible ordered phase. It finds six single-phase regions (α through ζ), including a high-temperature ε phase near x ≈ 0.83 that matches subtle steps in experimental voltage curves. The decisive bottleneck is the γ phase at x ≈ 0.5: strong calcium–vacancy ordering produces a migration barrier near 1.16 eV, while a two-phase γ+δ region (0.5 ≤ x ≤ 0.67) persists under ordinary battery temperatures. Together these features make full reversible extraction kinetically inaccessible at 298 K, limiting usable capacity to roughly half the theoretical value—exactly as observed. The paper therefore supplies both a microscopic explanation of the shortfall and concrete design levers (cation doping, particle-size reduction, elevated-temperature operation) to flatten the γ landscape and recover capacity.

Core claim

Accessible electrochemical capacity in CaV₂O₄ is kinetically limited to at most half the theoretical capacity at 298 K. The limit arises because calcium mobility is severely impeded in the γ phase (x ≈ 0.5; Em ≈ 1160 meV) while a persistent two-phase region between the δ (x ≈ 0.67) and γ phases is traversed under electrochemical conditions.

What carries the argument

Cluster-expansion Hamiltonian fitted to DFT formation energies, used in grand-canonical Monte Carlo to produce the finite-temperature phase diagram and voltage profiles, combined with nudged-elastic-band migration barriers on the ordered ground-state phases.

Load-bearing premise

That the calculated migration barriers (GGA for the main phases, unfine-tuned machine-learning estimates for the others) correctly rank which phases block calcium motion, even though the thermodynamics used a different density-functional method.

What would settle it

Direct measurement of calcium diffusivity or activation energy inside the ordered half-filled γ phase (or a doped analogue that disrupts the Ca-vacancy order), showing either a barrier far below ~1 eV or reversible extraction well past x = 0.5 at 298 K without kinetic arrest.

Watch this falsifier. Get emailed when new claim-graph text bears on it.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit.

Referee Report

2 major / 5 minor

Summary. This manuscript combines SCAN+U DFT, a cluster-expansion Hamiltonian (RMSE 13.4 meV/f.u., WCV 15.7 meV/f.u.), grand-canonical Monte Carlo, free-energy integration, and GGA-NEB (plus ML estimates for two compositions) to map the T–x phase diagram and Ca2+ migration barriers of post-spinel CaxV2O4 (0≤x≤1). It identifies six single-phase regions (α–ζ), including a high-T ε phase near x≈0.83 that appears via eutectic/peritectic-type reactions between ~370–590 K, and shows that a γ+δ two-phase field (0.5≤x≤0.67) persists well above room temperature. Combined with Em≈1160 meV in the ordered γ ground state versus ~600–660 meV in δ and ζ, the authors conclude that accessible capacity at 298 K is kinetically limited to at most half the theoretical value, consistent with Black et al.’s partial extraction, and suggest doping or particle-size reduction to mitigate the γ bottleneck.

Significance. The work supplies a concrete, experimentally aligned explanation for the limited capacity of a computationally screened Ca cathode and links phase stability to transport in a way that is actionable for materials design. Strengths include a carefully validated CE (ground-state recovery via CMC, free-energy integration for hysteresis), an explicit T–x diagram with invariant reactions that rationalize subtle experimental voltage features near x~0.83, and DFT-NEB barriers that rank the kinetic bottleneck. The half-capacity claim is falsifiable against existing operando XRD and temperature-dependent capacity data and offers clear follow-up strategies (doping, nanostructuring). If the ranking of barriers holds, the paper is a useful template for diagnosing kinetic traps in other multivalent intercalation hosts.

major comments (2)
  1. §2.4 and §3.5–3.6 (Fig. 6, Fig. S5): Thermodynamics are obtained with SCAN+U while all reported Em values (and the ranking that makes γ the bottleneck) use GGA-NEB, with only untuned MLIP/TL estimates for β and ε. The paper cites prior work that GGA captures qualitative Em trends, yet its own SI shows that the ML models do not systematically track DFT Em. A short consistency check—e.g., one SCAN+U or hybrid NEB path at the γ and δ ground states, or a clear statement of the expected error bar on the ~500 meV γ–δ gap—would make the kinetic-limit claim more robust without changing the qualitative conclusion.
  2. Eq. (2) and §2.3: The constant voltage offset ΔV is chosen so that the average GCMC voltage over 0≤x≤1 matches the 0 K DFT average of 2.73 V. This is a free parameter that affects absolute plateau heights (and the comparison to the experimental ~3.55 V average). The relative step structure and the existence of the ε-related feature are independent of ΔV, but the manuscript should state more explicitly which conclusions are invariant to the choice of ΔV and which are not.
minor comments (5)
  1. §3.5 and §3.6 both carry the heading “Voltage profiles”; the second should be retitled “Ca2+ migration barriers” (or similar).
  2. Fig. 5 inset: the voltage step is reported at a composition offset by ~0.001–0.002 from the ε stoichiometry; a brief note on residual GCMC sampling/hysteresis would help readers interpret the feature.
  3. Fig. 3: the y-axis break is useful but the dominant pair ECI (~202 meV) should be stated in the caption for readers who miss the break.
  4. §4: the LFP particle-size analogy is apt; a short sentence on whether the γ ordering is expected to survive under high-rate or nano-particle conditions would strengthen the design discussion.
  5. Data availability: the GitHub repository is mentioned; ensuring that the CE ECIs, GCMC free-energy integration scripts, and NEB endpoints are deposited would aid reproducibility.

Circularity Check

1 steps flagged

No significant circularity: phase diagram and Em are independent DFT/CE/MC/NEB outputs compared to external experiment; only a conventional voltage-offset alignment and a prior U value appear.

specific steps
  1. fitted input called prediction [§2.3 Methods, Equation 2]
    "V(x, T) = −µ(x, T)/z + ∆V where z = 2 is the valence of Ca2+. ∆V is a constant shift applied to align the average calculated voltage across the entire 0 ≤ x ≤ 1 range at any T with the reference average intercalation voltage of 2.73 V obtained from 0 K DFT calculations."

    The absolute voltage scale of all finite-T profiles is forced by construction to match the 0 K DFT average. This is a conventional rigid offset, not a free fit to experiment, and does not determine the phase boundaries or Em ranking that underwrite the half-capacity claim; it only affects absolute V values, which the paper already notes disagree with experiment.

full rationale

The central claim (accessible capacity kinetically limited to ~half theoretical at 298 K) is built from (i) a CE fitted to 262 SCAN+U formation energies, validated by RMSE/WCV and CMC ground-state search, then used in GCMC to produce a T–x phase diagram with a persistent γ+δ two-phase field, and (ii) independent GGA-NEB Em values that peak at the ordered γ ground state (~1160 meV). These are not defined in terms of the experimental capacity they are later compared to (Black et al.). The only mild self-referential steps are the constant ΔV shift that forces the average GCMC voltage to equal the 0 K DFT average of 2.73 V (Eq. 2) and the adoption of U = 1.0 eV from the authors’ prior SCAN+U work; both are standard practice and do not force the half-capacity conclusion, which rests on the phase-field topology and the Em ranking. MLIP/TL Em estimates for β/ε are acknowledged as unreliable and are not load-bearing. No uniqueness theorem, ansatz smuggled via self-citation, or fitted parameter renamed as prediction drives the result. Score 1 for the conventional voltage alignment only.

Axiom & Free-Parameter Ledger

2 free parameters · 4 axioms · 1 invented entities

Central claim rests on standard DFT/CE/MC/NEB methodology plus a few domain choices (U, GGA for barriers, neglect of vibrational free energy, voltage offset). No new physical entities beyond conventional phase labels; ε is a predicted phase with partial experimental voltage-profile support.

free parameters (2)
  • Hubbard U on V 3d = 1.0 eV
    Fixed at 1.0 eV from authors’ prior SCAN+U calibration; formation energies and hull depend on this choice.
  • Voltage offset ΔV = chosen to match 2.73 V average
    Constant shift so average GCMC voltage over 0≤x≤1 matches 0 K DFT average intercalation voltage of 2.73 V (Eq. 2); absolute plateau heights are not pure predictions.
axioms (4)
  • domain assumption SCAN+U formation energies of Ca–vacancy configurations are accurate enough for a transferable CE and finite-T phase diagram.
    Invoked throughout §2.1–2.3 and Fig. 2; U taken from prior work without re-benchmarking against experiment for this system.
  • domain assumption GGA-NEB yields reliable qualitative ranking of Ca migration barriers across compositions (threshold ~525–650 meV for usable mobility).
    Stated in §2.4 citing Devi et al.; used to declare γ and α kinetic bottlenecks while δ and ζ are acceptable (§3.5–3.6).
  • domain assumption Configurational free energy from classical GCMC on the CE Hamiltonian dominates phase stability; vibrational and electronic entropy contributions can be neglected for the T–x diagram.
    Implicit in §2.3 construction of Fig. 4; not tested with phonon free energies.
  • standard math Cluster expansion truncated to selected pairs/triplets/quadruplets with LASSO-fitted ECIs represents the DFT energy landscape near the hull.
    Standard CE formalism (Eq. 1); RMSE/WCV reported; outliers at EHull 50–200 meV/f.u. acknowledged in Fig. 2b.
invented entities (1)
  • ε phase (x∼0.83, stable ~370–590 K via eutectic/peritectic-type reactions) independent evidence
    purpose: Explains subtle experimental voltage slope changes near x~0.80–0.85 and fills the high-x phase diagram.
    Not a 0 K ground state; stabilized by configurational entropy in GCMC. Partial external handle via experimental voltage features; structure snapshot in SI/GitHub.

pith-pipeline@v1.1.0-grok45 · 21939 in / 3112 out tokens · 37412 ms · 2026-07-10T11:02:49.032832+00:00 · methodology

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read the original abstract

Calcium-ion batteries (CBs) represent an alternative to lithium-ion technology but their advancement is limited by the lack of high-performance intercalation cathodes. Identified via computational screening, post-spinel CaV$_2$O$_4$ has emerged as a promising candidate, though its practical application is hindered by limited electrochemical capacity. Hence, we investigate the thermodynamic and ionic transport characteristics of Ca$_x$V$_2$O$_4$ ($0 \leq x \leq 1$) in this work, by integrating the cluster expansion formalism with Monte Carlo simulations and density functional theory based calculations. We construct the temperature-composition phase diagram of Ca$_x$V$_2$O$_4$ revealing several stable phases ($\alpha$ through $\zeta$) that can appear during electrochemical operations at different voltages. Importantly, we observe the formation of the $\varepsilon$ phase at $x \sim 0.83$ across a 370-590~K temperature window via invariant reactions, which agrees with observations in the experimental voltage profiles. Further, migration barrier calculations confirm that Ca mobility is severely impeded within the $\alpha$ ($x \sim 0$) and $\gamma$ ($x \sim 0.5$) phases. With the strong Ca-vacancy ordering contributing to the high barrier in $\gamma$ and the persistent two-phase region stretching across the $\delta$ ($x \sim 0.67$) and the $\gamma$ phases, we expect the accessible electrochemical capacity in the CaV$_2$O$_4$ system to be kinetically limited to at most half the theoretical capacity at 298~K, in agreement with experiments. Strategies including cation doping and particle size reduction can be considered to flatten the potential energy landscape of $\gamma$ and improve Ca mobility. Our computational findings highlight the interplay between stability and transport and provide design strategies that can enable the practical use of CaV$_2$O$_4$ as a CB cathode.

Figures

Figures reproduced from arXiv: 2607.08224 by Dereje Bekele Tekliye, Gopalakrishnan Sai Gautam, Javeed Ahmad Dar.

Figure 1
Figure 1. Figure 1: Crystal structure of CaxV2O4. Teal and purple (in panel a) polyhedra denote the VO6 framework around V1 and V2 sites, respectively, while orange spheres denote the Ca sites. Dashed lines outline the simulation cell. (a) Conventional cell, (b) 1 × 1 × 2, and (c) 1 × 1 × 3 supercells. Post-spinel CaV2O4 adopts the orthorhombic CaFe2O4-type structure (space group Pnma) comprising two crystallographically dist… view at source ↗
Figure 2
Figure 2. Figure 2: a presents the 0 K convex hull of CaxV2O4, computed using DFT (orange line) and the fitted CE Hamiltonian (teal line). The formation energies are referenced to the fully intercalated (CaV2O4) and dein￾tercalated (V2O4) end members. Individual datapoints are shown as orange (DFT) and teal (CE) triangles, with larger symbols denoting structures that lie on the convex hull and are therefore thermodynamically … view at source ↗
Figure 3
Figure 3. Figure 3: Plot of ECIs, normalized by multiplicity, as a function of cluster size for Ca [PITH_FULL_IMAGE:figures/full_fig_p007_3.png] view at source ↗
Figure 4
Figure 4. Figure 4: Computed temperature-composition (T − x) phase diagram for the CaxV2O4 system. The colored regions represent the co-existence of two-phases that are separated by the single-phase regions (α through ζ). fairly negligible non-stoichiometry even at elevated temperatures (up to ∼ 590 K), further contributing to the persistence of the γ + δ two-phase region. The composition range between 0.67 ≤ x ≤ 1.0 displays… view at source ↗
Figure 5
Figure 5. Figure 5: Computed voltage profiles for Ca intercalation in Ca [PITH_FULL_IMAGE:figures/full_fig_p010_5.png] view at source ↗
Figure 6
Figure 6. Figure 6: DFT-based NEB calculated Ca2+ Em in CaxV2O4 at different x. Results for the endpoints (x = 0 and x = 1) are obtained Ref. 25, while the remaining Em are calculated in this work. Figure S5 compiles the Em estimates for the different ground states in CaxV2O4 obtained using machine learned models. x = 0.67 (δ phase), the Em increases marginally to ∼ 661 meV, indicating that the formation of the δ phase during… view at source ↗

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Reference graph

Works this paper leans on

68 extracted references · 68 canonical work pages · 2 internal anchors

  1. [1]

    Ultimate limits to intercalation reactions for lithium batteries.Chemical Reviews, 114(23):11414–11443, 2014

    M Stanley Whittingham. Ultimate limits to intercalation reactions for lithium batteries.Chemical Reviews, 114(23):11414–11443, 2014

    work page 2014

  2. [2]

    Towards greener and more sustainable batteries for electrical energy storage.Nature Chemistry, 7(1):19–29, 2015

    Dominique Larcher and Jean-Marie Tarascon. Towards greener and more sustainable batteries for electrical energy storage.Nature Chemistry, 7(1):19–29, 2015

    work page 2015

  3. [3]

    Rapidly falling costs of battery packs for electric vehicles.Nature Climate Change, 5(4):329–332, 2015

    Bj¨ orn Nykvist and M˚ ans Nilsson. Rapidly falling costs of battery packs for electric vehicles.Nature Climate Change, 5(4):329–332, 2015

    work page 2015

  4. [4]

    Is lithium the new gold?Nature Chemistry, 2(6):510–510, 2010

    Jean-Marie Tarascon. Is lithium the new gold?Nature Chemistry, 2(6):510–510, 2010

    work page 2010

  5. [5]

    Batteries and fuel cells for emerging electric vehicle markets.Nature Energy, 3(4):279–289, 2018

    Zachary P Cano, Dustin Banham, Siyu Ye, Andreas Hintennach, Jun Lu, Michael Fowler, and Zhongwei Chen. Batteries and fuel cells for emerging electric vehicle markets.Nature Energy, 3(4):279–289, 2018

    work page 2018

  6. [6]

    Odyssey of multivalent cathode materials: open questions and future challenges.Chemical Reviews, 117(5):4287–4341, 2017

    Pieremanuele Canepa, Gopalakrishnan Sai Gautam, Daniel C Hannah, Rahul Malik, Miao Liu, Kevin G Gallagher, Kristin A Persson, and Gerbrand Ceder. Odyssey of multivalent cathode materials: open questions and future challenges.Chemical Reviews, 117(5):4287–4341, 2017

    work page 2017

  7. [7]

    Multivalent rechargeable batteries.Energy Storage Materials, 20:253–262, 2019

    Alexandre Ponrouch, Jan Bitenc, Robert Dominko, Niklas Lindahl, Patrik Johansson, and M Rosa Palac´ ın. Multivalent rechargeable batteries.Energy Storage Materials, 20:253–262, 2019

    work page 2019

  8. [8]

    Scientific challenges for the implementation of zn-ion batteries.Joule, 4(4):771–799, 2020

    Lauren E Blanc, Dipan Kundu, and Linda F Nazar. Scientific challenges for the implementation of zn-ion batteries.Joule, 4(4):771–799, 2020

    work page 2020

  9. [9]

    Quest for nonaqueous multivalent secondary batteries: magnesium and beyond.Chemical Reviews, 114(23):11683–11720, 2014

    John Muldoon, Claudiu B Bucur, and Thomas Gregory. Quest for nonaqueous multivalent secondary batteries: magnesium and beyond.Chemical Reviews, 114(23):11683–11720, 2014

    work page 2014

  10. [10]

    Towards a calcium-based rechargeable battery.Nature Materials, 15(2):169–172, 2016

    Alexandre Ponrouch, Carlos Frontera, Fanny Bard´ e, and M Rosa Palac´ ın. Towards a calcium-based rechargeable battery.Nature Materials, 15(2):169–172, 2016

    work page 2016

  11. [11]

    Achieve- ments, challenges, and prospects of calcium batteries.Chemical Reviews, 120(14):6331–6357, 2019

    M Elena Arroyo-de Dompablo, Alexandre Ponrouch, Patrik Johansson, and M Rosa Palac´ ın. Achieve- ments, challenges, and prospects of calcium batteries.Chemical Reviews, 120(14):6331–6357, 2019

    work page 2019

  12. [12]

    Exploits, advances and challenges benefiting beyond li-ion battery technologies.Journal of Alloys and Compounds, 817:153261, 2020

    Abdel El Kharbachi, Olena Zavorotynska, M Latroche, Ferm` ın Cuevas, Volodymyr Yartys, and M Ficht- ner. Exploits, advances and challenges benefiting beyond li-ion battery technologies.Journal of Alloys and Compounds, 817:153261, 2020

    work page 2020

  13. [13]

    Da Wang, Xiangwen Gao, Yuhui Chen, Liyu Jin, Christian Kuss, and Peter G. Bruce. Plating and stripping calcium in an organic electrolyte.Nature Materials, 17(1):16–20, 2018

    work page 2018

  14. [14]

    Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries.Energy & Environmental Science, 12(12):3496–3501, 2019

    Zhenyou Li, Olaf Fuhr, Maximilian Fichtner, and Zhirong Zhao-Karger. Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries.Energy & Environmental Science, 12(12):3496–3501, 2019

    work page 2019

  15. [15]

    Current-density-dependent electroplating in ca electrolytes: From globules to dendrites.ACS Energy Letters, 5(7):2283–2290, 2020

    Shengda D Pu, Chen Gong, Xiangwen Gao, Ziyang Ning, Sixie Yang, John-Joseph Marie, Boyang Liu, Robert A House, Gareth O Hartley, Jun Luo, et al. Current-density-dependent electroplating in ca electrolytes: From globules to dendrites.ACS Energy Letters, 5(7):2283–2290, 2020. 16

    work page 2020

  16. [16]

    Reversible calcium plating and stripping at room temperature using a borate salt.ACS Energy Letters, 4(9):2271–2276, 2019

    Abhinandan Shyamsunder, Lauren E Blanc, Abdeljalil Assoud, and Linda F Nazar. Reversible calcium plating and stripping at room temperature using a borate salt.ACS Energy Letters, 4(9):2271–2276, 2019

    work page 2019

  17. [17]

    Multivalent batteries—prospects for high energy density: Ca batteries.Frontiers in Chemistry, 7:79, 2019

    Damien Monti, Alexandre Ponrouch, Rafael B Araujo, Fanny Barde, Patrik Johansson, and M Rosa Palac´ ın. Multivalent batteries—prospects for high energy density: Ca batteries.Frontiers in Chemistry, 7:79, 2019

    work page 2019

  18. [18]

    Calcium-ion batteries: current state-of-the-art and future perspectives.Advanced Materials, 30(39):1801702, 2018

    Rosalind J Gummow, George Vamvounis, M Bobby Kannan, and Yinghe He. Calcium-ion batteries: current state-of-the-art and future perspectives.Advanced Materials, 30(39):1801702, 2018

    work page 2018

  19. [19]

    Materials design rules for multivalent ion mobility in intercalation structures.Chemistry of Materials, 27(17):6016–6021, 2015

    Ziqin Rong, Rahul Malik, Pieremanuele Canepa, Gopalakrishnan Sai Gautam, Miao Liu, Anubhav Jain, Kristin Persson, and Gerbrand Ceder. Materials design rules for multivalent ion mobility in intercalation structures.Chemistry of Materials, 27(17):6016–6021, 2015

    work page 2015

  20. [20]

    Exploration of nasicon frameworks as calcium-ion battery electrodes

    Dereje Bekele Tekliye, Ankit Kumar, Xie Weihang, Thelakkattu Devassy Mercy, Pieremanuele Canepa, and Gopalakrishnan Sai Gautam. Exploration of nasicon frameworks as calcium-ion battery electrodes. Chemistry of Materials, 34(22):10133–10143, 2022

    work page 2022

  21. [21]

    Fluoride frameworks as potential calcium battery cathodes.Journal of Materials Chemistry A, 12(30):18993–19007, 2024

    Dereje Bekele Tekliye and Gopalakrishnan Sai Gautam. Fluoride frameworks as potential calcium battery cathodes.Journal of Materials Chemistry A, 12(30):18993–19007, 2024

    work page 2024

  22. [22]

    Searching ternary ox- ides and chalcogenides as positive electrodes for calcium batteries.Chemistry of Materials, 33(14):5809– 5821, 2021

    Wang Lu, Juefan Wang, Gopalakrishnan Sai Gautam, and Pieremanuele Canepa. Searching ternary ox- ides and chalcogenides as positive electrodes for calcium batteries.Chemistry of Materials, 33(14):5809– 5821, 2021

    work page 2021

  23. [23]

    Fister, Haesun Park, Bob Jin Kwon, Brian J

    Sanghyeon Kim, Liang Yin, Myeong Hwan Lee, Prakash Parajuli, Lauren Blanc, Timothy T. Fister, Haesun Park, Bob Jin Kwon, Brian J. Ingram, Peter Zapol, Robert F. Klie, Kisuk Kang, Linda F. Nazar, Saul H. Lapidus, and John T. Vaughey. High-voltage phosphate cathodes for rechargeable ca-ion batteries.ACS Energy Letters, 5(10):3203–3211, 10 2020

    work page 2020

  24. [24]

    Heo, Jooeun Hyoung, Hunho H

    Boosik Jeon, Jongwook W. Heo, Jooeun Hyoung, Hunho H. Kwak, Dongmin M. Lee, and Seung- Tae Hong. Reversible calcium-ion insertion in nasicon-type nav2(po4)3.Chemistry of Materials, 32(20):8772–8780, 10 2020

    work page 2020

  25. [25]

    Ashley P Black, Carlos Frontera, Arturo Torres, Miguel Recio-Poo, Patrick Rozier, Juan D Forero- Saboya, Fran¸ cois Fauth, Esteban Urones-Garrote, M Elena Arroyo-de Dompablo, and M Rosa Palac´ ın. Elucidation of the redox activity of ca 2mno3.5 and cav 2o4 in calcium batteries using operando xrd: charge compensation mechanism and reversibility.Energy Stor...

    work page 2022

  26. [26]

    Geometry-based Discovery of Calcium Battery Cathodes Accelerated by Foundational Machine-Learned Models

    Dereje Bekele Tekliye, Achinthya Krishna Bheemaguli, and Gopalakrishnan Sai Gautam. Geometry- based discovery of calcium battery cathodes accelerated by foundational machine-learned models.arXiv preprint arXiv:2605.29029, 2026

    work page internal anchor Pith review Pith/arXiv arXiv 2026

  27. [27]

    Inhomogeneous electron gas.Physical Review, 136(3B):B864, 1964

    Pierre Hohenberg and Walter Kohn. Inhomogeneous electron gas.Physical Review, 136(3B):B864, 1964

    work page 1964

  28. [28]

    Self-consistent equations including exchange and correlation effects

    Walter Kohn and Lu Jeu Sham. Self-consistent equations including exchange and correlation effects. Physical Review, 140(4A):A1133, 1965. 17

    work page 1965

  29. [29]

    Generalized cluster description of multicom- ponent systems.Physica A: Statistical Mechanics and its Applications, 128(1-2):334–350, 1984

    Juan M Sanchez, Francois Ducastelle, and Denis Gratias. Generalized cluster description of multicom- ponent systems.Physica A: Statistical Mechanics and its Applications, 128(1-2):334–350, 1984

    work page 1984

  30. [30]

    Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points.The Journal of chemical physics, 113(22):9978– 9985, 2000

    Graeme Henkelman and Hannes J´ onsson. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points.The Journal of chemical physics, 113(22):9978– 9985, 2000

    work page 2000

  31. [31]

    Optimization methods for finding minimum energy paths.The Journal of chemical physics, 128(13), 2008

    Daniel Sheppard, Rye Terrell, and Graeme Henkelman. Optimization methods for finding minimum energy paths.The Journal of chemical physics, 128(13), 2008

    work page 2008

  32. [32]

    Ab initio molecular dynamics for liquid metals.Physical review B, 47(1):558, 1993

    Georg Kresse and J¨ urgen Hafner. Ab initio molecular dynamics for liquid metals.Physical review B, 47(1):558, 1993

    work page 1993

  33. [33]

    Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Physical Review B, 54(16):11169, 1996

    Georg Kresse and J¨ urgen Furthm¨ uller. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Physical Review B, 54(16):11169, 1996

    work page 1996

  34. [34]

    Strongly constrained and appropriately normed semilocal density functional.Physical Review Letters, 115(3):036402, 2015

    Jianwei Sun, Adrienn Ruzsinszky, and John P Perdew. Strongly constrained and appropriately normed semilocal density functional.Physical Review Letters, 115(3):036402, 2015

    work page 2015

  35. [35]

    Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+Ustudy.Physical Review B, 57(3):1505, 1998

    Sergei L Dudarev, Gianluigi A Botton, Sergey Y Savrasov, CJ Humphreys, and Adrian P Sutton. Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+Ustudy.Physical Review B, 57(3):1505, 1998

    work page 1998

  36. [36]

    Band theory and mott insulators: HubbardU instead of stonerI.Physical Review B, 44(3):943, 1991

    Vladimir I Anisimov, Jan Zaanen, and Ole K Andersen. Band theory and mott insulators: HubbardU instead of stonerI.Physical Review B, 44(3):943, 1991

    work page 1991

  37. [37]

    Evaluating transition metal oxides within DFT- SCAN and SCAN+Uframeworks for solar thermochemical applications.Physical Review Materials, 2(9):095401, 2018

    Gopalakrishnan Sai Gautam and Emily A Carter. Evaluating transition metal oxides within DFT- SCAN and SCAN+Uframeworks for solar thermochemical applications.Physical Review Materials, 2(9):095401, 2018

    work page 2018

  38. [38]

    Evaluating optimalUfor 3d transition-metal oxides within the SCAN+Uframework.Physical Review Materials, 4(4):045401, 2020

    Olivia Y Long, Gopalakrishnan Sai Gautam, and Emily A Carter. Evaluating optimalUfor 3d transition-metal oxides within the SCAN+Uframework.Physical Review Materials, 4(4):045401, 2020

    work page 2020

  39. [39]

    Accuracy of metagga functionals in describing transition metal fluorides.Physical Review Materials, 8(9):093801, 2024

    Dereje Bekele Tekliye and Gopalakrishnan Sai Gautam. Accuracy of metagga functionals in describing transition metal fluorides.Physical Review Materials, 8(9):093801, 2024

    work page 2024

  40. [40]

    Performance of the r2scan functional in transition metal oxides.Journal of chemical theory and computation, 19(13):4202–4215, 2023

    S Swathilakshmi, Reshma Devi, and Gopalakrishnan Sai Gautam. Performance of the r2scan functional in transition metal oxides.Journal of chemical theory and computation, 19(13):4202–4215, 2023

    work page 2023

  41. [41]

    From ultrasoft pseudopotentials to the projector augmented-wave method.Physical Review B, 59(3):1758, 1999

    Georg Kresse and Daniel Joubert. From ultrasoft pseudopotentials to the projector augmented-wave method.Physical Review B, 59(3):1758, 1999

    work page 1999

  42. [42]

    Improved tetrahedron method for brillouin-zone integrations.Physical Review B, 49(23):16223, 1994

    Peter E Bl¨ ochl, Ove Jepsen, and Ole Krogh Andersen. Improved tetrahedron method for brillouin-zone integrations.Physical Review B, 49(23):16223, 1994

    work page 1994

  43. [43]

    Special points for brillouin-zone integrations.Physical Review B, 13(12):5188, 1976

    Hendrik J Monkhorst and James D Pack. Special points for brillouin-zone integrations.Physical Review B, 13(12):5188, 1976

    work page 1976

  44. [44]

    The inorganic crystal structure database (ICSD)—present and future.Crystal- lography Reviews, 10(1):17–22, 2004

    Mariette Hellenbrandt. The inorganic crystal structure database (ICSD)—present and future.Crystal- lography Reviews, 10(1):17–22, 2004. 18

    work page 2004

  45. [45]

    Python materials genomics (pymatgen): A robust, open-source python library for materials analysis.Computational Materials Science, 68:314–319, 2013

    Shyue Ping Ong, William Davidson Richards, Anubhav Jain, Geoffroy Hautier, Michael Kocher, Shreyas Cholia, Dan Gunter, Vincent L Chevrier, Kristin A Persson, and Gerbrand Ceder. Python materials genomics (pymatgen): A robust, open-source python library for materials analysis.Computational Materials Science, 68:314–319, 2013

    work page 2013

  46. [46]

    Die berechnung optischer und elektrostatischer gitterpotentiale.Annalen der physik, 369(3):253–287, 1921

    Paul P Ewald. Die berechnung optischer und elektrostatischer gitterpotentiale.Annalen der physik, 369(3):253–287, 1921

    work page 1921

  47. [47]

    Casm—a software package for first-principles based study of multi- component crystalline solids.Computational Materials Science, 217:111897, 2023

    Brian Puchala, John C Thomas, Anirudh Raju Natarajan, Jon Gabriel Goiri, Sesha Sai Behara, Jonas L Kaufman, and Anton Van der Ven. Casm—a software package for first-principles based study of multi- component crystalline solids.Computational Materials Science, 217:111897, 2023

    work page 2023

  48. [48]

    First-principles statistical mechanics of multicomponent crystals.Annual Review of Materials Research, 48(1):27–55, 2018

    Anton Van der Ven, John C Thomas, Brian Puchala, and Anirudh Raju Natarajan. First-principles statistical mechanics of multicomponent crystals.Annual Review of Materials Research, 48(1):27–55, 2018

    work page 2018

  49. [49]

    Thermodynamics of the zr-o system from first-principles calculations

    B Puchala and A Van der Ven. Thermodynamics of the zr-o system from first-principles calculations. Physical Review B—Condensed Matter and Materials Physics, 88(9):094108, 2013

    work page 2013

  50. [50]

    Equation of state calculations by fast computing machines.The journal of chemical physics, 21(6):1087–1092, 1953

    Nicholas Metropolis, Arianna W Rosenbluth, Marshall N Rosenbluth, Augusta H Teller, and Edward Teller. Equation of state calculations by fast computing machines.The journal of chemical physics, 21(6):1087–1092, 1953

    work page 1953

  51. [51]

    Axel Van De Walle and Mark Asta. Self-driven lattice-model monte carlo simulations of alloy thermody- namic properties and phase diagrams.Modelling and Simulation in Materials Science and Engineering, 10(5):521–538, 2002

    work page 2002

  52. [52]

    Phase transitions in the lini0

    Yoyo Hinuma, Ying S Meng, Kisuk Kang, and Gerbrand Ceder. Phase transitions in the lini0. 5mn0. 5o2 system with temperature.Chemistry of Materials, 19(7):1790–1800, 2007

    work page 2007

  53. [53]

    Temperature-concentration phase diagram of p 2-na x coo 2 from first-principles calculations.Physical Review B—Condensed Matter and Materials Physics, 77(22):224111, 2008

    Yoyo Hinuma, Ying S Meng, and Gerbrand Ceder. Temperature-concentration phase diagram of p 2-na x coo 2 from first-principles calculations.Physical Review B—Condensed Matter and Materials Physics, 77(22):224111, 2008

    work page 2008

  54. [54]

    Phase transformations and volume changes in spinel lixmn2o4.Solid State Ionics, 135(1-4):21–32, 2000

    A Van der Ven, C Marianetti, D Morgan, and G Ceder. Phase transformations and volume changes in spinel lixmn2o4.Solid State Ionics, 135(1-4):21–32, 2000

    work page 2000

  55. [55]

    Linking the electronic structure of solids to their thermodynamic and kinetic properties.Mathematics and computers in simulation, 80(7):1393–1410, 2010

    Anton Van der Ven, John C Thomas, Qingchuan Xu, and Jishnu Bhattacharya. Linking the electronic structure of solids to their thermodynamic and kinetic properties.Mathematics and computers in simulation, 80(7):1393–1410, 2010

    work page 2010

  56. [56]

    Generalized gradient approximation made simple.Physical review letters, 77(18):3865, 1996

    John P Perdew, Kieron Burke, and Matthias Ernzerhof. Generalized gradient approximation made simple.Physical review letters, 77(18):3865, 1996

    work page 1996

  57. [57]

    Effect of exchange- correlation functionals on the estimation of migration barriers in battery materials.npj Computational Materials, 8(1):160, 2022

    Reshma Devi, Baltej Singh, Pieremanuele Canepa, and Gopalakrishnan Sai Gautam. Effect of exchange- correlation functionals on the estimation of migration barriers in battery materials.npj Computational Materials, 8(1):160, 2022. 19

    work page 2022

  58. [58]

    A Niazi, Sergey L Bud’ko, Deborah L Schlagel, JQ Yan, Thomas A Lograsso, A Kreyssig, S Das, S Nandi, AI Goldman, Andreas Honecker, et al. Single-crystal growth, crystallography, magnetic susceptibility, heat capacity, and thermal expansion of the antiferromagnetic s= 1 chain compound cav 2 o 4.Physical Review B—Condensed Matter and Materials Physics, 79(1...

    work page 2009

  59. [59]

    The design space of e (3)-equivariant atom- centred interatomic potentials.Nature Machine Intelligence, 7(1):56–67, 2025

    Ilyes Batatia, Simon Batzner, D´ avid P´ eter Kov´ acs, Albert Musaelian, Gregor NC Simm, Ralf Drautz, Christoph Ortner, Boris Kozinsky, and G´ abor Cs´ anyi. The design space of e (3)-equivariant atom- centred interatomic potentials.Nature Machine Intelligence, 7(1):56–67, 2025

    work page 2025

  60. [60]

    Orb-v3: atomistic simulation at scale

    Benjamin Rhodes, Sander Vandenhaute, Vaidotas ˇSimkus, James Gin, Jonathan Godwin, Tim Duignan, and Mark Neumann. Orb-v3: atomistic simulation at scale.arXiv preprint arXiv:2504.06231, 2025

    work page internal anchor Pith review Pith/arXiv arXiv 2025

  61. [61]

    Leveraging transfer learning for accurate estimation of ionic migration barriers in solids.npj Computational Materials, 2026

    Reshma Devi, Keith T Butler, and Gopalakrishnan Sai Gautam. Leveraging transfer learning for accurate estimation of ionic migration barriers in solids.npj Computational Materials, 2026

    work page 2026

  62. [62]

    Kinetics of non-equilibrium lithium incorporation in lifepo4.Nature materials, 10(8):587–590, 2011

    Rahul Malik, Fei Zhou, and Gerbrand Ceder. Kinetics of non-equilibrium lithium incorporation in lifepo4.Nature materials, 10(8):587–590, 2011

    work page 2011

  63. [63]

    Configurational electronic entropy and the phase dia- gram of mixed-valence oxides:¡? format?¿ the case of li x fepo 4.Physical review letters, 97(15):155704, 2006

    Fei Zhou, Thomas Maxisch, and Gerbrand Ceder. Configurational electronic entropy and the phase dia- gram of mixed-valence oxides:¡? format?¿ the case of li x fepo 4.Physical review letters, 97(15):155704, 2006

    work page 2006

  64. [64]

    Capturing metastable structures during high-rate cycling of lifepo4 nanopar- ticle electrodes.Science, 344(6191):1252817, 2014

    Hao Liu, Fiona C Strobridge, Olaf J Borkiewicz, Kamila M Wiaderek, Karena W Chapman, Peter J Chupas, and Clare P Grey. Capturing metastable structures during high-rate cycling of lifepo4 nanopar- ticle electrodes.Science, 344(6191):1252817, 2014

    work page 2014

  65. [65]

    Phase behavior in rhombohedral nasi- con electrolytes and electrodes.Chemistry of Materials, 32(18):7908–7920, 2020

    Zeyu Deng, Gopalakrishnan Sai Gautam, Sanjeev Krishna Kolli, Jean-No¨ el Chotard, Anthony K Cheetham, Christian Masquelier, and Pieremanuele Canepa. Phase behavior in rhombohedral nasi- con electrolytes and electrodes.Chemistry of Materials, 32(18):7908–7920, 2020

    work page 2020

  66. [66]

    Phase stability and sodium-vacancy orderings in a nasicon electrode.Journal of Materials Chemistry A, 10(1):209–217, 2022

    Ziliang Wang, Sunkyu Park, Zeyu Deng, Dany Carlier, Jean-No¨ el Chotard, Laurence Croguennec, Gopalakrishnan Sai Gautam, Anthony K Cheetham, Christian Masquelier, and Pieremanuele Canepa. Phase stability and sodium-vacancy orderings in a nasicon electrode.Journal of Materials Chemistry A, 10(1):209–217, 2022

    work page 2022

  67. [67]

    Thermodynamics of sodium–lead alloys for negative electrodes from first-principles.Chemistry of Materials, 36(14):6831– 6837, 2024

    Damien KJ Lee, Zeyu Deng, Gopalakrishnan Sai Gautam, and Pieremanuele Canepa. Thermodynamics of sodium–lead alloys for negative electrodes from first-principles.Chemistry of Materials, 36(14):6831– 6837, 2024

    work page 2024

  68. [68]

    Understanding and optimizing li substitution in p2-type sodium layered oxides for sodium-ion batteries.Advanced Functional Materials, page 2425499, 2025

    Mingfeng Xu, Giovanni Gammaitoni, Michael H¨ afner, Eduardo Villalobos-Portillo, Carlo Marini, and Matteo Bianchini. Understanding and optimizing li substitution in p2-type sodium layered oxides for sodium-ion batteries.Advanced Functional Materials, page 2425499, 2025. 20

    work page 2025