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Abstract
We study the performance of multiconfiguration pairdensity functional theory (MCPDFT) and multireference perturbation theory for the computation of the bond dissociation energies in 12 transitionmetalcontaining diatomic molecules and three small transitionmetalcontaining polyatomic molecules and in two transitionmetal dimers. The first step is a multiconfiguration selfconsistentfield calculation, for which two choices must be made: (i) the active space and (ii) its partition into subspaces, if the generalized active space formulation is used. In the present work, the active space is chosen systematically by using three correlatedparticipatingorbitals (CPO) schemes, and the partition is chosen by using the separatedpair (SP) approximation. Our calculations show that MCPDFT generally has similar accuracy to CASPT2, and the activespace dependence of MCPDFT is not very great for transitionmetalligand bond dissociation energies. We also find that the SP approximation works very well, and in particular SP with the fully translated BLYP functional SPftBLYP is more accurate than CASPT2. SP greatly reduces the number of configuration state functions relative to CASSCF. For the cases of FeO and NiO with extendedCPO active space, for which complete active space calculations are unaffordable, SP calculations are not only affordable but also of satisfactory accuracy. All of the MCPDFT results are significantly better than the corresponding results with brokensymmetry spinunrestricted KohnSham density functional theory. Finally we test a perturbation theory method based on the SP reference and find that it performs slightly worse than CASPT2 calculations, and for most cases of the nominalCPO active space, the approximate SP perturbation theory calculations are less accurate than the much less expensive SPPDFT calculations.
Original language  English (US) 

Pages (fromto)  616626 
Number of pages  11 
Journal  Journal of Chemical Theory and Computation 
Volume  13 
Issue number  2 
DOIs  
State  Published  Feb 14 2017 
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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