Stochastic coupled cluster theory: Efficient sampling of the coupled cluster expansion
Journal of Chemical Physics
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Scott, C., & Thom, A. (2017). Stochastic coupled cluster theory: Efficient sampling of the coupled cluster expansion. Journal of Chemical Physics, 147 (124105)https://doi.org/10.1063/1.4991795
We consider the sampling of the coupled cluster expansion within stochastic coupled cluster theory. Observing the limitations of previous approaches due to the inherently non-linear behavior of a coupled cluster wavefunction representation, we propose new approaches based on an intuitive, well-defined condition for sampling weights and on sampling the expansion in cluster operators of different excitation levels. We term these modifications even and truncated selections, respectively. Utilising both approaches demonstrates dramatically improved calculation stability as well as reduced computational and memory costs. These modifications are particularly effective at higher truncation levels owing to the large number of terms within the cluster expansion that can be neglected, as demonstrated by the reduction of the number of terms to be sampled when truncating at triple excitations by 77% and hextuple excitations by 98%.
Is supplemented by: https://doi.org/10.17863/CAM.13149
C.J.C.S. is grateful to the Sims Fund for a studentship and A.J.W.T. to the Royal Society for a University Research Fellowship under Grant No. UF110161. Both are grateful for support under ARCHER Leadership Project Grant No. e507.
Royal Society (uf110161)
External DOI: https://doi.org/10.1063/1.4991795
This record's URL: https://www.repository.cam.ac.uk/handle/1810/267473