Abstract

Ab initio pseudo-atomic orbital (PAO) Hamiltonians express the electronic structure of a solid in a compact, localized basis that spans the same Hilbert space as a conventional Slater–Koster tight-binding model, thereby providing an exact ab initio representation without any loss of accuracy. Building on this correspondence, we develop an environment-dependent tight-binding (EDTB) framework in which Slater–Koster hopping integrals are augmented with bond-screening functions that capture the local coordination environment. All parameters are determined by fitting to the PAO eigenvalue spectrum across multiple atomic configurations simultaneously, which breaks the degeneracy between screening and hopping parameters and yields physically meaningful, transferable models capable of generating Hamiltonians for large systems with ab initio precision. We demonstrate the efficiency and accuracy of the approach on four prototypical systems: bulk platinum, silicon surfaces, Si/Ge [001] superlattices, and twisted bilayer graphene with up to 4,324 atoms. The method is implemented in the paoflow code and integrates seamlessly with its full post-processing suite, enabling the evaluation of a broad range of electronic, optical, and transport properties.

Abstract

Ab initio pseudo-atomic orbital (PAO) Hamiltonians express the electronic structure of a solid in a compact, localized basis that spans the same Hilbert space as a conventional Slater–Koster tight-binding model, thereby providing an exact ab initio representation without any loss of accuracy. Building on this correspondence, we develop an environment-dependent tight-binding (EDTB) framework in which Slater–Koster hopping integrals are augmented with bond-screening functions that capture the local coordination environment. All parameters are determined by fitting to the PAO eigenvalue spectrum across multiple atomic configurations simultaneously, which breaks the degeneracy between screening and hopping parameters and yields physically meaningful, transferable models capable of generating Hamiltonians for large systems with ab initio precision. We demonstrate the efficiency and accuracy of the approach on four prototypical systems: bulk platinum, silicon surfaces, Si/Ge [001] superlattices, and twisted bilayer graphene with up to 4,324 atoms. The method is implemented in the paoflow code and integrates seamlessly with its full post-processing suite, enabling the evaluation of a broad range of electronic, optical, and transport properties.

Abstract

Ab initio pseudo-atomic orbital (PAO) Hamiltonians express the electronic structure of a solid in a compact, localized basis that spans the same Hilbert space as a conventional Slater–Koster tight-binding model, thereby providing an exact ab initio representation without any loss of accuracy. Building on this correspondence, we develop an environment-dependent tight-binding (EDTB) framework in which Slater–Koster hopping integrals are augmented with bond-screening functions that capture the local coordination environment. All parameters are determined by fitting to the PAO eigenvalue spectrum across multiple atomic configurations simultaneously, which breaks the degeneracy between screening and hopping parameters and yields physically meaningful, transferable models capable of generating Hamiltonians for large systems with ab initio precision. We demonstrate the efficiency and accuracy of the approach on four prototypical systems: bulk platinum, silicon surfaces, Si/Ge [001] superlattices, and twisted bilayer graphene with up to 4,324 atoms. The method is implemented in the paoflow code and integrates seamlessly with its full post-processing suite, enabling the evaluation of a broad range of electronic, optical, and transport properties.

Abstract

Ab initio pseudo-atomic orbital (PAO) Hamiltonians express the electronic structure of a solid in a compact, localized basis that spans the same Hilbert space as a conventional Slater–Koster tight-binding model, thereby providing an exact ab initio representation without any loss of accuracy. Building on this correspondence, we develop an environment-dependent tight-binding (EDTB) framework in which Slater–Koster hopping integrals are augmented with bond-screening functions that capture the local coordination environment. All parameters are determined by fitting to the PAO eigenvalue spectrum across multiple atomic configurations simultaneously, which breaks the degeneracy between screening and hopping parameters and yields physically meaningful, transferable models capable of generating Hamiltonians for large systems with ab initio precision. We demonstrate the efficiency and accuracy of the approach on four prototypical systems: bulk platinum, silicon surfaces, Si/Ge [001] superlattices, and twisted bilayer graphene with up to 4,324 atoms. The method is implemented in the paoflow code and integrates seamlessly with its full post-processing suite, enabling the evaluation of a broad range of electronic, optical, and transport properties.