Renormalized Internally Contracted Multireference Coupled Cluster with Perturbative Triples

In this work, we combine the many-body formulation of the internally contracted multireference coupled cluster (ic-MRCC) method with Evangelista’s multireference formulation of the driven similarity renormalization group (DSRG). The DSRG method can be viewed as a unitary multireference coupled cluster theory, which renormalizes the amplitudes based on a flow equation approach to eliminate numerical instabilities. We extend this approach by demonstrating that the unitary flow equation approach can be adapted for nonunitary transformations, rationalizing the renormalization of ic-MRCC amplitudes. We denote the new approach, the renormalized ic-MRCC (ric-MRCC) method. To achieve high accuracy with a reasonable computational cost, we introduce a new approximation to the Baker–Campbell–Hausdorff expansion. We fully consider the linear commutator while approximating the quadratic commutator, for which we neglect specific contractions involving amplitudes with active indices. Moreover, we introduce approximate perturbative triples to obtain the ric-MRCCSD[T] method. We demonstrate the accuracy of our approaches in comparison to advanced multireference methods for the potential energy curves of H8, F2, H2O, N2, and Cr2. Additionally, we show that ric-MRCCSD and ric-MRCSSD[T] match the accuracy of CCSD(T) for evaluating spectroscopic constants and of full configuration interaction energies for a set of small molecules.

• Publication year

  2024

• Venue

  Journal of Chemical Theory and Computation

• Publication date

  2024-05-25

• Fields of study

  Medicine, Physics

• Identifiers
  DOI 10.1021/acs.jctc.4c00679arXiv 2405.16139PMID 39158160PMCID 11360144
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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