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Enabling Ab Initio Molecular Dynamics under Bias: The CP2K+SMEAGOL Interface for Integrating Density Functional Theory and Non-Equilibrium Green Functions.

ABSTRACT: Density functional theory (DFT) combined with non-equilibrium Green's functions (NEGF) is a powerful approach to model quantum transport under external bias potentials at reasonable computational cost. In this work, we present a new interface between the popular mixed Gaussian/plane waves electronic structure package, CP2K, and the NEGF, code SMEAGOL, the most feature-rich implementation of DFT-NEGF available for CP2K to date. The CP2K+SMEAGOL interface includes the implementation of current induced forces. We verify this implementation for a variety of systems: an infinite 1D Au wire, a parallel-plate capacitor, and a Au-H₂-Au junction. We find good agreement with SMEAGOL calculations performed with SIESTA for the same systems and with the example of a solvated Au wire demonstrating for the first time that DFT-NEGF can be used to perform molecular dynamics simulations under bias of large-scale condensed phase systems under realistic operating conditions.

SUBMITTER: Ahart CS

PROVIDER: S-EPMC11325543 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Enabling Ab Initio Molecular Dynamics under Bias: The CP2K+SMEAGOL Interface for Integrating Density Functional Theory and Non-Equilibrium Green Functions.

Ahart Christian S CS Chulkov Sergey K SK Cucinotta Clotilde S CS

Journal of chemical theory and computation 20240716 15

Density functional theory (DFT) combined with non-equilibrium Green's functions (NEGF) is a powerful approach to model quantum transport under external bias potentials at reasonable computational cost. In this work, we present a new interface between the popular mixed Gaussian/plane waves electronic structure package, CP2K, and the NEGF, code SMEAGOL, the most feature-rich implementation of DFT-NEGF available for CP2K to date. The CP2K+SMEAGOL interface includes the implementation of current ind ...[more]

PMID: 39013589

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Project description:Ligand field theory (LFT) is one of the cornerstones of coordination chemistry since it provides a conceptual framework in which a great many properties of d- and f-element compounds can be discussed. While LFT serves as a powerful qualitative guide, it is not a tool for quantitative predictions on individual compounds since it incorporates semiempirical parameters that must be fitted to experiment. One way to connect the realms of first-principles electronic structure theory that has emerged as particularly powerful over the past decade is the ab initio ligand field theory (AILFT). The original formulation of this method involved the extraction of LFT parameters by fitting the ligand field Hamiltonian to a complete active space self-consistent field (CASSCF) Hamiltonian. The extraction was shown to be unique provided that the active space consists of 5/7 metal d/f-based molecular orbitals (MOs). Subsequent improvements have involved incorporating dynamical correlation using second-order N-electron valence state perturbation theory (NEVPT2) or second-order dynamical correlation dressed complete active space (DCDCAS). However, the limitation of past approaches is that the method requires a minimal space of 5/7 metal d- or f-based molecular orbitals. This leads to a number of limitations: (1) neglect of radial or semicore correlation would arise from the effect of a second d-shell or an sp-shell in the active space, (2) a more balanced description of metal-ligand bond covalency is lacking because the bonding ligand-based counterparts of the metal d/f orbitals are not in the active space. This usually leads to an exaggerated ionicity of the M-L bonds. In this work, we present an extended active space AILFT (esAILFT) that circumvents these limitations and is, in principle, applicable to arbitrary active spaces, as long as these contain the 5/7 metal d/f-based MOs as a subset. esAILFT was implemented in a development version of the ORCA software package. In order to help with the application of the new method, various criteria for active space extension were explored for 3d, 4d, and 5d transition-metal ions with varying charge. An interpretation of the trends in the Racah B parameter for these ions is also presented as a demonstration of the capabilities of esAILFT.

Dataset Information

Enabling Ab Initio Molecular Dynamics under Bias: The CP2K+SMEAGOL Interface for Integrating Density Functional Theory and Non-Equilibrium Green Functions.

Publications

Enabling Ab Initio Molecular Dynamics under Bias: The CP2K+SMEAGOL Interface for Integrating Density Functional Theory and Non-Equilibrium Green Functions.

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