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Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory
Michał Hapka1, Łukasz Rajchel2, Marcin Modrzejewski1
1Faculty of Chemistry, University of Warsaw, 02-093 Warsaw, Pasteura 1, Poland.
The Journal of Chemical Physics
|October 10, 2014
Summary
Optimally tuned long-range corrected (LRC) functionals improve symmetry-adapted perturbation theory (SAPT) calculations. This method minimizes self-interaction error, enhancing the accuracy of interaction energy components for various systems.
Area of Science:
- Quantum Chemistry
- Computational Physics
Background:
- Symmetry-Adapted Perturbation Theory (SAPT) is crucial for calculating intermolecular interactions.
- Accurate description of monomers is vital for reliable SAPT energy components.
- Long-Range Corrected (LRC) functionals offer potential improvements in electronic structure calculations.
Purpose of the Study:
- To evaluate the performance of optimally tuned LRC functionals within the SAPT framework.
- To assess the impact of generalized Kohn-Sham (GKS) descriptions on SAPT interaction energies.
- To compare LRC-based SAPT with traditional methods.
Main Methods:
- Application of optimally tuned LRC functionals to SAPT.
- Evaluation of second-order energy components at the coupled level.
- Utilizing generalized Kohn-Sham (GKS) and standard Kohn-Sham (KS) descriptions for monomers.
- Testing on polyacetylene chains and stretched He3(+) systems.
Main Results:
- Optimally tuned LRC functionals, particularly with GKS, significantly improve SAPT interaction energy components.
- Minimization of many-electron self-interaction error is key to this improvement.
- LRC-based SAPT yields results comparable or superior to asymptotically corrected functionals.
- Comparison highlights the benefits of GKS over KS for monomer description in SAPT.
Conclusions:
- Optimally tuned LRC functionals are essential for high-quality SAPT calculations, especially when using GKS.
- The GKS approach with LRC functionals effectively reduces self-interaction errors.
- LRC-SAPT presents a promising advancement over existing methods for studying intermolecular forces.
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