Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms

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Although many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. However, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree-Fock method have been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive element, electron affinity of the electronegative bonding partner (EA), atomic excitation energy (EE) to prepare the valence states of the interacting partners, and interaction energy (IE) of the valence-prepared states. Adding Hartree-Fock exchange helps to obtain better results for atomic excitation energy, and this leads to improvements in getting the right answer for the right reason. The following functionals are singled out for reasonably good performance on all three of bond distance, BDE, and dipole moment: B97-1, B97-3, MPW1B95, M05, M06, M06-2X, M08-SO, N12-SX, O3LYP, TPSS, τ-HCTHhyb, and GAM; all but two (TPSS and GAM) of these functionals are hybrid functionals.

Original languageEnglish (US)
Pages (from-to)2968-2983
Number of pages16
JournalJournal of Chemical Theory and Computation
Issue number7
StatePublished - May 26 2015

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