Skip to content
DraconiticResearch
Search Sources API
197,357 studies31 sourcesUpdated 2 min ago
Peer-reviewedCC BYJournal of chemical theory and computation

Periodic GFN2-xTB in CP2K: Multipolar Ewald Electrostatics, k-Point Sampling, and Transferability Benchmarks for Solids.

  • Vahideh Alizadeh1,2
  • Johann Pototschnig1,2
  • Leopold M Seidler3
  • Sebastian Ehlert4
  • Thomas D Kühne1,2,5
5 affiliations
  1. 1Center for Advanced Systems Understanding (CASUS), Conrad-Schiedt-Straße 20, Görlitz02826, Germany.
  2. 2Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, Dresden01328, Germany.
  3. 3Mulliken Center for Theoretical Chemistry, Universität Bonn, Beringstraße 4, Bonn53115, Germany.
  4. 4AI for Science, Microsoft Research, Karl-Liebknecht-Str. 32, Berlin10178, Germany.
  5. 5Institute of Artificial Intelligence, Technische Universität Dresden, Helmholtzstraße 10, Dresden01069, Germany.
Read full textPDFDOICite

Abstract

Extended tight-binding methods are attractive for condensed-phase simulations because they retain an explicit electronic Hamiltonian at a cost far below conventional density functional theory. Their transferability to periodic materials, however, cannot be assessed reliably without a genuinely periodic Hamiltonian, Brillouin-zone sampling, and symmetry-aware crystal calculations. We present a periodic implementation of the second-generation geometry, frequency, and noncovalent interaction parametrization of extended tight binding (GFN2-xTB) in CP2K. The central theoretical ingredient is a multipolar Ewald formulation for the self-consistent shell charges, atomic dipoles, and quadrupoles of GFN2-xTB, together with analytical forces and stress contributions for geometry optimization, cell optimization, and molecular dynamics. For the ranking of ice polymorphs in the DMC-ICE13 data set, periodic GFN2-xTB on a converged 33k-point mesh improves the relative polymorph energies over GFN1-xTB, reducing the mean absolute error from 8.01 to 3.46 kJ mol-1. Because GFN1-xTB and GFN2-xTB differ in several coupled, jointly parametrized terms, this whole-model comparison does not isolate the contribution of multipolar electrostatics. For the LC10 set of cubic covalent and ionic solids, GFN2-xTB yields valid equation-of-state minima for all ten systems, with lattice-constant and cohesive-energy mean absolute errors of 0.062 Å and 1.30 eV per atom, respectively. Periodic GFN2-xTB is evaluated for molecular crystal lattice energies and cell parameters using the X23b data set. Using native Bloch 23-mesh cell optimization with full symmetry reduction, followed by a 33-mesh energy evaluation on the optimized cells, periodic GFN2-xTB gives a mean absolute lattice-energy error of 14.09 kJ mol-1 and a mean absolute relaxed-cell volume error of 5.84% for the full X23b relaxed-cell set. The benchmarks position periodic GFN2-xTB as an efficient electronic structure level for screening, pre-optimization, and large exploratory simulations. This work creates the foundation for periodic anisotropic electrostatics in the extended tight-binding framework and their efficient application in CP2K.

Related

  1. Terahertz lattice imprint of a hidden multipolar ordering transition in Gd2Ru2O7
    Nicolas M. Kawahala, Rafael L. Sabainsk, Esteban Marulanda +2
    Physical Review ResearchPeer-reviewedPublisher termsFull textCondensed matterCrossrefDOAJAPS
  2. Multipolar exchange in a many-body homonuclear mixture of atoms in different internal states
    M. Bulakhov, A. S. Peletminskii, Yu. V. Slyusarenko
    arXivPreprintarXiv licenceFull textAtomic, molecular & optical physicsCondensed matterarXiv
  3. Static multipolar Einstein-vector-Gauss-Bonnet black holes
    Burkhard Kleihaus, Jutta Kunz
    arXivPreprintCC BY 4.0Full textGravitation & general relativityHigh-energy & particle physicsarXiv
  4. Static multipolar Einstein-vector-Gauss-Bonnet black holes
    Burkhard Kleihaus, Jutta Kunz
    Physics Letters BPeer-reviewedCC BY 4.0Full textHigh-energy & particle physicsCrossrefDOAJ
  5. Electrostatics of Chern junctions in a magnetic field
    Robin Durand, Pascal Simon, Ion Garate
    arXivPreprintarXiv licenceFull textCondensed matterarXiv

Cite

BibTeXRIS
BibTeX
@article{alizadeh2026periodic,
  title = {{Periodic GFN2-xTB in CP2K: Multipolar Ewald Electrostatics, k-Point Sampling, and Transferability Benchmarks for Solids.}},
  author = {Vahideh Alizadeh and Johann Pototschnig and Leopold M Seidler and Sebastian Ehlert and Thomas D Kühne},
  journal = {Journal of chemical theory and computation},
  year = {2026},
  month = sep,
  doi = {10.1021/acs.jctc.6c01034},
  url = {https://europepmc.org/article/MED/42917474},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Periodic GFN2-xTB in CP2K: Multipolar Ewald Electrostatics, k-Point Sampling, and Transferability Benchmarks for Solids.
AU  - Vahideh Alizadeh
AU  - Johann Pototschnig
AU  - Leopold M Seidler
AU  - Sebastian Ehlert
AU  - Thomas D Kühne
PY  - 2026
DA  - 2026/09/01
JO  - Journal of chemical theory and computation
DO  - 10.1021/acs.jctc.6c01034
UR  - https://europepmc.org/article/MED/42917474
AB  - Extended tight-binding methods are attractive for condensed-phase simulations because they retain an explicit electronic Hamiltonian at a cost far below conventional density functional theory. Their transferability to periodic materials, however, cannot be assessed reliably without a genuinely periodic Hamiltonian, Brillouin-zone sampling, and symmetry-aware crystal calculations. We present a periodic implementation of the second-generation geometry, frequency, and noncovalent interaction parametrization of extended tight binding (GFN2-xTB) in CP2K. The central theoretical ingredient is a multipolar Ewald formulation for the self-consistent shell charges, atomic dipoles, and quadrupoles of GFN2-xTB, together with analytical forces and stress contributions for geometry optimization, cell optimization, and molecular dynamics. For the ranking of ice polymorphs in the DMC-ICE13 data set, periodic GFN2-xTB on a converged 33k-point mesh improves the relative polymorph energies over GFN1-xTB, reducing the mean absolute error from 8.01 to 3.46 kJ mol-1. Because GFN1-xTB and GFN2-xTB differ in several coupled, jointly parametrized terms, this whole-model comparison does not isolate the contribution of multipolar electrostatics. For the LC10 set of cubic covalent and ionic solids, GFN2-xTB yields valid equation-of-state minima for all ten systems, with lattice-constant and cohesive-energy mean absolute errors of 0.062 Å and 1.30 eV per atom, respectively. Periodic GFN2-xTB is evaluated for molecular crystal lattice energies and cell parameters using the X23b data set. Using native Bloch 23-mesh cell optimization with full symmetry reduction, followed by a 33-mesh energy evaluation on the optimized cells, periodic GFN2-xTB gives a mean absolute lattice-energy error of 14.09 kJ mol-1 and a mean absolute relaxed-cell volume error of 5.84% for the full X23b relaxed-cell set. The benchmarks position periodic GFN2-xTB as an efficient electronic structure level for screening, pre-optimization, and large exploratory simulations. This work creates the foundation for periodic anisotropic electrostatics in the extended tight-binding framework and their efficient application in CP2K.
SN  - 1549-9618
SN  - 1549-9626
ER  -