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Augmenting Large Language Models via Vector Embeddings to Improve Domain-Specific Responsiveness
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Toward the "Gold Standard" in Bootstrap Embedding.

Yi Sun1

  • 1Department of Chemistry, Chicago Center for Theoretical Chemistry, James Franck Institute, and Institute for Biophysical Dynamics, The University of Chicago, Chicago, Illinois 60637, United States.

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|October 28, 2025
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Summary
This summary is machine-generated.

We developed a computationally efficient Coupled Cluster Singles, Doubles, and Perturbative Triples (CCSD(T)) method using Bootstrap Embedding (BE2). This approach accurately calculates relative energies for large molecular systems, enabling routine applications previously limited by computational cost.

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Area of Science:

  • Quantum chemistry
  • Computational physics
  • Theoretical chemistry

Background:

  • Coupled Cluster Singles, Doubles, and Perturbative Triples (CCSD(T)) is a highly accurate quantum chemistry method.
  • Conventional CCSD(T) calculations are computationally expensive, limiting their application to small systems.
  • Fragment-based methods offer a potential solution for scaling correlated wave function calculations.

Purpose of the Study:

  • To implement and validate a computationally efficient CCSD(T) density matrix evaluation within the Bootstrap Embedding (BE2) framework.
  • To accelerate CCSD(T) calculations using orbital permutation symmetry.
  • To enable accurate and routine application of CCSD(T) to larger molecular systems.

Main Methods:

  • Implementation of CCSD(T) density matrix evaluation integrated with the Bootstrap Embedding (BE2) framework.
  • Acceleration of calculations using orbital permutation symmetry.
  • Benchmarking against canonical all-electron CCSD(T) calculations and using Intrinsic Atomic Orbital and Projected Atomic Orbital (IAO + PAO) partitioning.

Main Results:

  • The BE2-CCSD(T) approach significantly reduces computational cost compared to canonical CCSD(T).
  • Accurate relative energies were obtained, with benchmark calculations on annulene systems showing near-linear scaling with system size.
  • The method demonstrates high accuracy for isomerizations when using IAO + PAO partitioning.

Conclusions:

  • The BE2-CCSD(T) method provides a computationally feasible and accurate alternative to conventional CCSD(T) for large systems.
  • This work enables the routine application of high-accuracy correlated wave function methods to previously intractable molecular systems.
  • The developed framework lays the foundation for extending fragment-based correlated methods in quantum chemistry.