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Updated: Dec 16, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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Size-extensive seniority-zero energy functionals derived from configuration interaction with double excitations.

Nam Vu1, A Eugene DePrince1

  • 1Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA.

The Journal of Chemical Physics
|July 3, 2020
PubMed
Summary
This summary is machine-generated.

The pair two-electron reduced density matrix (pp2RDM) approach accurately approximates doubly occupied configuration interaction (DOCI) energies. This method offers a more efficient and accurate alternative to traditional coupled-cluster methods for describing electron correlation.

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Area of Science:

  • Quantum chemistry
  • Computational physics
  • Materials science

Background:

  • The doubly occupied configuration interaction (DOCI) approach accurately describes nondynamic electron correlation but is computationally expensive.
  • Pair coupled-cluster doubles (pCCD) offers a more efficient alternative, but its accuracy can be limited.
  • Seniority-zero methods provide approximations to DOCI at lower computational costs.

Purpose of the Study:

  • To develop and evaluate seniority-zero formulations of quantum chemistry methods.
  • To compare the accuracy and efficiency of these new methods against established approaches like pCCD and DOCI.
  • To investigate the suitability of the pair two-electron reduced density matrix (pp2RDM) approach for approximating DOCI energies.

Main Methods:

  • Development of seniority-zero formulations for coupled-electron pair approximation, averaged coupled-pair functional, averaged quadratic coupled-cluster, and p2RDM.
  • Implementation and testing of these methods on molecular systems.
  • Comparison of calculated energies and reduced density matrices (RDMs) with DOCI and pCCD results.

Main Results:

  • The pp2RDM approach yields energies comparable in quality to pCCD and DOCI.
  • Seniority-zero Hermitian methods offer advantages over pCCD, including fewer parameters and simpler RDMs.
  • pp2RDM-derived RDMs provide better approximations to DOCI RDMs than those from pCCD.

Conclusions:

  • The pp2RDM method is a promising, computationally efficient approach for accurately describing nondynamic electron correlation.
  • This work advances the development of accurate and scalable quantum chemistry methods.
  • pp2RDM offers a superior alternative to pCCD for approximating DOCI results in molecular systems.