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Abstract
KohnSham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for openshell systems, the KohnSham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pairdensity functional theory (MCPDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the ontop density functional, that depends on the density and the ontop pair density calculated from this wave function. We also proposed a simple way to approximate the ontop density functional by translation of KohnSham exchangecorrelation functionals. The method is much less expensive than other postSCF methods for calculating the dynamical correlation energy starting with a multiconfiguration selfconsistentfield wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of maingroup molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MCPDFT, as compared to 6.9 kcal/mol for KohnSham theory with a comparable density functional. MCPDFT is more accurate on average than complete active space secondorder perturbation theory (CASPT2) for maingroup smallmolecule bond energies, alkyl bond dissociation energies, transitionmetalligand bond energies, proton affinities, and the water dimerization energy.
Original language  English (US) 

Pages (fromto)  8290 
Number of pages  9 
Journal  Journal of Chemical Theory and Computation 
Volume  11 
Issue number  1 
DOIs  
State  Published  Jan 13 2015 
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Projects
 1 Finished

Energy Frontier Research Center For Inorganometallic Catalyst Design (DESC0012702)
Gagliardi, L., Cramer, C., Lu, C. C., Penn, L. (., Stein, A. & Truhlar, D. G.
United States Department of Energy
8/1/14 → 7/31/18
Project: Research project