Full configuration interaction quantum Monte Carlo benchmark and multireference coupled cluster studies of tetramethyleneethane diradical

Veis, L. and Antalík, A. and Legeza, Örs and Alavi, A. and Pittner, J. (2018) Full configuration interaction quantum Monte Carlo benchmark and multireference coupled cluster studies of tetramethyleneethane diradical. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 14 (5). pp. 2439-2445. ISSN 1549-9618

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Abstract

We have performed a FCI-quality benchmark calculation for the tetramethyleneethane molecule in cc-pVTZ basis set employing a subset of CASPT2(6,6) natural orbitals for the FCIQMC calculation. The results are in an excellent agreement with the previous large scale diffusion Monte Carlo calculations by Pozun et al. and available experimental results. Our computations verified that there is a maximum on PES of the ground singlet state (1A) 45∘ torsional angle and the corresponding vertical singlet-triplet energy gap is 0.01 eV. We have employed this benchmark for assessment of the accuracy of MkCCSDT and DMRG-tailored CCSD (TCCSD) methods. MR MkCCSDT with CAS(2,2) model space, though giving good values for the singlet-triplet energy gap, is not able to properly describe the shape of the multireference singlet PES. Similarly, DMRG(24,25) is not able to correctly capture the shape of the singlet surface, due to the missing dynamic correlation. On the other hand, the DMRG-tailored CCSD method describes the shape of the ground singlet state with an excellent accuracy, but for the correct ordering requires computation of the zero-spin-projection component of the triplet state (3B1).

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