Natural Orbitals for Wave Function Based Correlated Calculations Using a Plane Wave Basis Set

Autor(en)

Andreas Grüneis, George H. Booth, Martijn Marsman, James Spencer, Ali Alavi, Georg Kresse

Abstrakt

We demonstrate that natural orbitals allow for reducing the computational cost of wave function based correlated calculations, especially for atoms and molecules in a large box, when a plane wave basis set under periodic boundary conditions is used. The employed natural orbitals are evaluated on the level of second-order Moller-Plesset perturbation theory (MP2), which requires a computational effort that scales as O(N(5)), where N is a measure of the system size. Moreover, we find that a simple approximation reducing the scaling to O(N(4)) yields orbitals that allow for a similar reduction of the number of virtual orbitals. The MP2 natural orbitals are applied to coupled-cluster singles and doubles (CCSD) as well as full configuration interaction Quantum Monte Carlo calculations of the H(2) molecule to test our implementation. Finally, the atomization energies of the LiH molecule and solid are calculated on the level of MP2 and CCSD.

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

University of Cambridge, Imperial College London

Journal

Journal of Chemical Theory and Computation

Band

7

Seiten

2780-2785

Anzahl der Seiten

6

ISSN

1549-9618

DOI

https://doi.org/10.1021/ct200263g

Publikationsdatum

2011

Peer-reviewed

Ja

ÖFOS 2012

103009 Festkörperphysik, 103025 Quantenmechanik, 103018 Materialphysik, 104022 Theoretische Chemie

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/8053ba41-e949-4142-9c1b-6d4efa8ec5e5