Search arXiv⌕ Search
Home/Archive/arXiv

arXiv · physics/0402086

Broken-Symmetry Unrestricted Hybrid Density Functional Calculations on Nickel Dimer and Nickel Hydride

Cristian V. Diaconu·Art E. Cho·J. D. Doll·David L. Freeman
View original source ↗Read source document ↗Export metadata ↓

Abstract

In the present work we investigate the adequacy of broken-symmetry unrestricted density functional theory (DFT) for constructing the potential energy curve of nickel dimer and nickel hydride, as a model for larger bare and hydrogenated nickel cluster calculations. We use three hybrid functionals: the popular B3LYP, Becke's newest optimized functional Becke98, and the simple FSLYP functional (50% Hartree-Fock and 50% Slater exchange and LYP gradient-corrected correlation functional) with two basis sets: all-electron (AE) Wachters+f basis set and Stuttgart RSC effective core potential (ECP) and basis set. We find that, overall, the best agreement with experiment, comparable to that of the high-level CASPT2, is obtained with B3LYP/AE, closely followed by Becke98/AE and Becke98/ECP. FSLYP/AE and B3LYP/ECP give slightly worse agreement with experiment, and FSLYP/ECP is the only method among the ones we studied that gives an unaceptably large error, underestimating the dissociation energy of nickel dimer by 28%, and being in the largest disagreement with the experiment and the other theoretical predictions.

Explore related subjects

physics.chem-phphysics.atm-clusphysics.atom-ph

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Cristian V. Diaconu, Art E. Cho, J. D. Doll, David L. Freeman. 2004-08-06. Broken-Symmetry Unrestricted Hybrid Density Functional Calculations on Nickel Dimer and Nickel Hydride. https://doi.org/10.1063/1.1798992

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

Construction of downfolded Hamiltonians from projective transcorrelation

Projective transcorrelation recovers the short-range electron correlation by a similarity transformation with a geminal function $f(r_{12})$, at the cost of an effective Hamiltonian containing a 3-body term. We replace the term by an effective operator of rank at most two, obtained from the two-body cumulant (2C) approximation to the three-particle reduced density matrix. The 2C 3-body energy is written without cumulants, and the effective one- and two-body interactions are derived as its partial derivatives with respect to the reduced density matrices. The truncation is assessed on the atomization and reaction energies of the HEAT set with CCSD(T), and on the CAS-pTC model, whose downfolded Hamiltonian is held on a qubit register with the number of Pauli strings reduced from the sixth power of the orbital count to the fourth.

physics.chem-ph↗
arXiv2026

Competing Ring-Opening and Hofmann Elimination Pathways in Aqueous TEMPO Catholytes: A First-Principles Study

Aqueous redox-flow batteries based on TEMPO derivatives are promising for large-scale energy storage, but their practical use is limited by the chemical instability of the oxidized N -oxoammonium state. In this work, we investigate the degradation of five TEMPO derivatives using ab initio molecular dynamics combined with enhanced sampling. Two proposed degradation mechanisms, ring opening and Hofmann elimination, are examined and their corresponding activation free energies are compared. For all derivatives considered, ring opening exhibits a lower activation free energy than Hofmann elimination, identifying it as the kinetically preferred degradation pathway. The magnitude of the ring-opening barrier, however, varies significantly between molecules, showing that different functionalizations strongly influence its stability toward degradation. The predicted preference for ring opening is consistent with available experimental studies, which have identified or inferred ring-opening degradation for several TEMPO-based catholytes. These results provide an atomistic picture of degradation pathways that are difficult to resolve experimentally and highlight the importance of molecular structure in controlling the kinetic stability of TEMPO derivatives in aqueous electrolytes.

physics.chem-ph↗
arXiv2026

Exchange-Correlation Potentials and Energies from Inverse Generalized Kohn-Sham Calculations

The Kohn-Sham (KS) formulation of density functional theory (DFT) is a map from the many-electron problem to an effective single-electron problem that is governed by a local multiplicative potential. The generalized-Kohn-Sham (GKS) formalism extends it to permit any single-electron operator---nonlocal, local non-multiplicative, local multiplicative, or any combination of them. Doing so expands the scope and ease of modeling the exchange-correlation (XC) functional in DFT, which encodes the complicated many-electron interactions into a mean-field of the electron density. However, unlike KS theory, development of XC functionals in GKS theory has been hindered by the absence of corresponding exact XC potentials and energies. We present the exact XC potentials and energies for atoms and molecules by solving the inverse GKS problem, using highly accurate correlated \textit{ab initio} densities. Our approach is validated across weakly and strongly correlated systems. We further examine a common, yet untested, assumption that KS and GKS correlation potentials and energies are similar, finding instead that they differ substantially in strongly correlated systems. Overall, this work offers a powerful tool to model next-generation of XC functionals within the GKS formalism of DFT.

physics.chem-ph↗