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The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
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Related Experiment Video

Updated: Jan 18, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Assessing the Reliability of Truncated Coupled Cluster Wave Function: Estimating the Distance from the Exact

Ádám Ganyecz1, Zsolt Benedek2,3, Klára Petrov4

  • 1Strongly Correlated Systems "Lendület" Research Group, Wigner Research Centre for Physics, H-1525, Budapest, Hungary.

Journal of Chemical Theory and Computation
|September 12, 2025
PubMed
Summary
This summary is machine-generated.

A new metric quantifies the accuracy of truncated wave function methods by measuring their distance from the exact full configuration interaction (FCI) solution. This approach offers a unique, cost-effective quality measure for computational chemistry methods.

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Area of Science:

  • Quantum Chemistry
  • Computational Chemistry

Background:

  • Truncated wave function methods are widely used but their accuracy is difficult to assess.
  • Existing diagnostics often compare derived properties rather than the wave function itself.

Purpose of the Study:

  • To develop a novel method for evaluating the reliability of truncated wave function approximations.
  • To quantify the deviation of approximate solutions from the exact full configuration interaction (FCI) wave function.

Main Methods:

  • Utilized the density matrix renormalization group (DMRG) to obtain an approximate FCI solution.
  • Introduced new metrics (d̃Φ, d̃γ) based on comparing low-level CI expansions and one-body reduced density matrices.
  • Benchmarked the approach using the CCSD method on the W4-17 dataset and transition-metal compounds.

Main Results:

  • Demonstrated the applicability of the new diagnostic for the CCSD method.
  • Showcased that the proposed metric is cost-effective, wave function-based, and independent of existing multireference measures.
  • Explored the impact of CCSD natural orbitals on the metric and active space size.

Conclusions:

  • The developed metric provides a unique and practical way to assess the quality of wave function approximations.
  • This diagnostic tool has broad applicability to various post-Hartree-Fock methods.
  • It offers a potential quality measure for computational chemistry calculations.