Driven similarity renormalization group: Third-order multireference perturbation theory.

Abstract

A third-order multireference perturbation theory based on the driven similarity renormalization group (DSRG-MRPT3) approach is presented. The DSRG-MRPT3 method has several appealing features: (a) it is intruder free, (b) it is size consistent, (c) it leads to a non-iterative algorithm with O(N6) scaling, and (d) it includes reference relaxation effects. The DSRG-MRPT3 scheme is benchmarked on the potential energy curves of F2, H2O2, C2H6, and N2 along the F-F, O-O, C-C, and N-N bond dissociation coordinates, respectively. The nonparallelism errors of DSRG-MRPT3 are consistent with those of complete active space third-order perturbation theory and multireference configuration interaction with singles and doubles and show significant improvements over those obtained from DSRG second-order multireference perturbation theory. Our efficient implementation of the DSRG-MRPT3 based on factorized electron repulsion integrals enables studies of medium-sized open-shell organic compounds. This point is demonstrated with computations of the singlet-triplet splitting (ΔST=ET-ES) of 9,10-anthracyne. At the DSRG-MRPT3 level of theory, our best estimate of the adiabatic ΔST is 3.9 kcal mol-1, a value that is within 0.1 kcal mol-1 from multireference coupled cluster results.