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In the present work we investigate the adequacy of broken-symmetry unrestricted density functional theory 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 unacceptably large error, underestimating the dissociation energy of Ni2 by 28%, and being in the largest disagreement with the experiment and the other theoretical predictions. We also find that for Ni2, the spin projection for the broken-symmetry unrestricted singlet states changes the ordering of the states, but the splittings are less than 10 meV. All our calculations predict a δδ-hole ground state for Ni2 and δ-hole ground state for NiH. Upon spin projection of the singlet state of Ni2 , almost all of our calculations: Becke98 and FSLYP both AE and ECP and B3LYP/AE predict 1 ( d A x2-y2d B x2-y2 d B ) or 1 ( d A xy d Bxy ) ground state, which is a mixture of 1 Σg + and 1Γg. B3LYP/ECP predicts a 3(d Ax 2 - y 2 d Bxy )(mixture of 3Σ g - and 3Γu ) ground state virtually degenerate with the 1 (d Ax2 - y 2 dB x 2 - y 2 )/ 1 (dAxy dBxy ) state. The doublet δ-hole ground state of NiH predicted by all our calculations is in agreement with the experimentally predicted 2 ^ ground state. For Ni2 , all our results are consistent with the experimentally predicted 0g+ (a mixture of l Σg+and 3Σ g-) or 0u-(a mixture of l Σu-and Σu +).

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© 2004 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Diaconu, Christian V., Art E. Choi, J. D. Doll and David L. Freeman. ʺBroken-Symmetry Unrestricted Hybrid Density Functional Calculations on Nickel Dimer and Nickel Hydride.ʺ Journal of Chemical Physics. 121(20):10026-10040. November 22, 2004. and may be found at