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A localized basis that allows fast and accurate second-order Moller-Plesset calculations
Joseph E Subotnik1, Martin Head-Gordon
1Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, USA.
The Journal of Chemical Physics
|March 3, 2005
Summary
We developed a new computational method using localized orbitals to achieve highly accurate Moller-Plesset perturbation theory (MP2) energies. This approach, Kapuy
Area of Science:
- Computational Chemistry
- Quantum Chemistry
- Electronic Structure Theory
Background:
- Accurate calculation of electron correlation is crucial for predicting molecular properties.
- Traditional methods for correlated calculations can be computationally expensive, scaling poorly with system size.
Purpose of the Study:
- To develop a computationally efficient method for accurate correlated energy calculations.
- To introduce a novel approach based on localized orthonormal orbitals and a modified Hamiltonian partitioning.
Main Methods:
- Computation of localized orthonormal orbitals (occupied and virtual).
- Representation of the Fock matrix in the localized orbital basis, achieving high diagonal dominance.
- Calculation of second-order Moller-Plesset (MP2) energies using Kapuy's method (KMP2).
Main Results:
- Empirically demonstrated that the localized orbitals are sufficient for highly accurate MP2 energies.
- The KMP2 method exhibits a favorable scaling, at most quadratic with potential for linearity, with the number of electrons.
Conclusions:
- The presented KMP2 algorithm offers a viable pathway for local-correlation calculations.
- This method provides a balance between accuracy and computational efficiency for electronic structure problems.