Hybrid correlation models based on active-space partitioning: correcting second-order Moller-Plesset perturbation theory for bond-breaking reactions.
Moller-Plesset second-order (MP2) perturbation theory breaks down at molecular geometries which are far away from equilibrium. We decompose the MP2 energy into contributions from different orbital subspaces and show that the divergent behavior of the MP2 energy comes from the excitations located within a small (or sometimes even the minimal) active space. The divergent behavior of the MP2 energy at large interfragment distances may be corrected by replacing a small number of terms by their more robust counterparts from coupled-cluster (CCSD) theory. We investigated several schemes of such a substitution, and we find that a coupling between the active-space CCSD and the remaining MP2 amplitudes is necessary to obtain the best results. This naturally leads us to an approach which has previously been examined in the context of cost-saving approximations to CCSD for equilibrium properties by Nooijen [J. Chem. Phys. 111, 10815 (1999)]. The hybrid MP2-CCSD approach, which has the same formal scaling as conventional MP2 theory, provides potential curves with a correct shape for bond-breaking reactions of BH, CH(4), and HF. The error of the MP2-CCSD method (measured against full configuration-interaction data) is smaller than that of MP2 at all interfragment separations and is qualitatively similar to that of full CCSD.
Bochevarov
Arteum D
AD
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Sherrill
C David
CD
D000465:Algorithms; D003198:Computer Simulation; D004735:Energy Transfer; D008956:Models, Chemical; D008958:Models, Molecular; D013223:Statistics as Topic