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Linear-scaling calculation of Hartree-Fock exchange energy with Non-orthogonal Generalised Wannier Functions
Abstrakt
We present a method for the calculation of four-centre two-electron repulsion integrals in terms of localised non-orthogonal generalised Wannier functions (NGWFs). Our method has been imple- mented in the ONETEP program and is used to compute the Hartree-Fock exchange energy component of Hartree-Fock and Density Functional Theory (DFT) calculations with hybrid exchange-correlation functionals. As the NGWFs are optimised in situ in terms of a systematically improvable basis set which is equivalent to plane waves, it is possible to achieve large basis set accuracy in routine cal- culations. The spatial localisation of the NGWFs allows us to exploit the exponential decay of the density matrix in systems with a band gap in order to compute the exchange energy with a compu- tational effort that increases linearly with the number of atoms. We describe the implementation of this approach in the ONETEP program for linear-scaling first principles quantum mechanical calcula- tions. We present extensive numerical validation of all the steps in our method. Furthermore, we find excellent agreement in energies and structures for a wide variety of molecules when comparing with other codes. We use our method to perform calculations with the B3LYP exchange-correlation func- tional for models of myoglobin systems bound with O2 and CO ligands and confirm that the same qualitative behaviour is obtained as when the same myoglobin models are studied with the DFT+U approach which is also available in ONETEP. Finally, we confirm the linear-scaling capability of our method by performing calculations on polyethylene and polyacetylene chains of increasing length.
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Autorzy (3)
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Q. Hill
- .. ...
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Chris-Kriton Skylaris
- University of Southampton School of Chemistry
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Pełna treść
- Wersja publikacji
- Accepted albo Published Version
- DOI:
- Cyfrowy identyfikator dokumentu elektronicznego (otwiera się w nowej karcie) 10.1063/1.4832338
- Licencja
- Copyright (2013 AIP Publishing LLC)
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Informacje szczegółowe
- Kategoria:
- Publikacja w czasopiśmie
- Typ:
- artykuł w czasopiśmie wyróżnionym w JCR
- Opublikowano w:
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JOURNAL OF CHEMICAL PHYSICS
nr 139,
ISSN: 0021-9606 - Język:
- angielski
- Rok wydania:
- 2013
- Opis bibliograficzny:
- Dziedzic J., Hill Q., Skylaris C.: Linear-scaling calculation of Hartree-Fock exchange energy with Non-orthogonal Generalised Wannier Functions// JOURNAL OF CHEMICAL PHYSICS. -Vol. 139, nr. 21 (2013),
- DOI:
- Cyfrowy identyfikator dokumentu elektronicznego (otwiera się w nowej karcie) 10.1063/1.4832338
- Weryfikacja:
- Politechnika Gdańska
wyświetlono 109 razy
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