A sequential transformation approach to the internally contracted multireference coupled cluster method

作者：Evangelista Francesco A^*; Hanauer Matthias; Koehn Andreas; Gauss Juergen

来源：Journal of Chemical Physics, 2012, 136(20): 204108.

DOI：10.1063/1.4718704

The internally contracted multireference coupled cluster (ic-MRCC) approach is formulated using a new wave function ansatz based on a sequential transformation of the reference sqic-MRCC). This alternative wave function simplifies the formulation of computationally viable methods while preserving the accuracy of the ic-MRCC approach. The structure of the sqic-MRCC wave function allows folding the effect of the single excitations into a similarity-transformed Hamiltonian whose particle rank is equal to the one of the Hamiltonian. Consequently, we formulate an approximation to the sqic-MRCC method with singles and doubles (included respectively up to fourfold and twofold commutators, sqic-MRCCSD[2]) that contains all terms present in the corresponding single-reference coupled cluster scheme. Computations of the potential energy curves for the dissociation of BeH2 show that the untruncated sqic-MRCCSD scheme yields results that are almost indistinguishable from the ordinary ic-MRCCSD method. The energy obtained from the computationally less expensive sqic-MRCCSD[2] approximation is found to deviate from the full ic-MRCCSD method by less than 0.2 mE(h) for BeH2, while, in the case of water, the harmonic vibrational frequencies of ozone, the singlet-triplet splitting of p-benzyne, and the dissociation curve of N-2, sqic-MRCCSD[2] faithfully reproduces the results obtained via the ic-MRCCSD scheme truncated to two commutators. A formal proof is given of the equivalence of the ic-MRCC and sqic-MRCC methods with the internally contracted and full configuration interaction approaches.

• 出版日期2012-5-28