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Electron Correlation from the Adiabatic Connection for Multireference Wave Functions.

Katarzyna Pernal1

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This study introduces an adiabatic connection formula for electron correlation energy, efficiently calculating dynamic correlation using only one- and two-electron reduced density matrices for multireference wave functions.

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Area of Science:

  • Quantum Chemistry
  • Computational Chemistry
  • Electronic Structure Theory

Background:

  • Electron correlation energy is crucial for accurate molecular property prediction.
  • Multireference wave functions are necessary for strongly correlated systems.
  • Existing methods for calculating correlation energy can be computationally expensive.

Purpose of the Study:

  • Derive a general adiabatic connection (AC) formula for electron correlation energy.
  • Develop an efficient method for calculating dynamic correlation energy in multireference systems.
  • Enable correlation energy calculation from reduced density matrices.

Main Methods:

  • Derivation of an adiabatic connection formula for electron correlation energy.
  • Coupling the AC formalism with the extended random phase approximation.
  • Utilizing generalized valence bond perfect pairing model for a closed-form expression.

Main Results:

  • The AC formula recovers dynamic correlation energy with balanced treatment.
  • Correlation energy can be determined from one- and two-electron reduced density matrices.
  • An approximate AC formula yields an overall M^5 computational cost scaling.

Conclusions:

  • The developed method provides an efficient multireference approach for dynamic electron correlation.
  • The method is suitable for strongly correlated systems.
  • Calculation of correlation energy from reduced density matrices simplifies the process.