Full implementation and benchmark studies of Mukherjee's state-specific multireference coupled-cluster ansatz

Das, Sanghamitra and Mukherjee, Debashis and Kállay, Mihály (2010) Full implementation and benchmark studies of Mukherjee's state-specific multireference coupled-cluster ansatz. JOURNAL OF CHEMICAL PHYSICS, 132 (7). pp. 1-13. ISSN 0021-9606

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Abstract

The state-specific multireference coupled-cluster (SS-MRCC) ansatz developed by Mukherjee and co-workers [J. Chem. Phys. 110, 6171 (1999)] has been implemented by means of string-based techniques. The implementation is general and allows for using arbitrary complete active spaces of any spin multiplicity and arbitrarily high excitations in the cluster operators. Several test calculations have been performed for single- and multiple-bond dissociations of molecular systems. Our experience shows that convergence problems are encountered when solving the working equations of the SS-MRCC in the case the weight of one or more reference functions tends to take on very small values. This is system specific and cannot yet be handled in a black-box fashion. The problem can be obviated by either dropping all the cluster amplitudes from the corresponding model functions with coefficients below a threshold or by a regularization procedure suggested by Tikhonov or a combination of both. In the current formulation the SS-MRCC is not invariant with respect to transformation of active orbitals among themselves. This feature has been extensively explored to test the degree of accuracy of the computed energies with both pseudocanonical and localized active orbitals. The performance of the method is assessed by comparing the results with the corresponding full configuration interaction (CI) values with the same set of orbitals (correlated and frozen). Relative efficacies of CI methods such as MRCI singles and doubles with the same active space and size-extensivity corrected ones such as MR averaged coupled pair functional and MR averaged quadratic CC have also been studied. Allied full-fledged CC methods have also been employed to see their relative performance vis-agrave-vis the SS-MRCC. These latter methods are the complete-active-space-inspired single-reference (SR) CC based SS theory and the single-root MR Brillouin-Wigner CC. Our benchmark results indicate that the performance of the SS-MRCC is generally quite good for localized active orbitals. The performance with the pseudocanonical orbitals, however, is sometimes not as satisfactory as for the localized orbitals.

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