The evaluation of exact exchange (EXX) is an important component of quantum chemical calculations performed with ab initio and hybrid density functional methods. While evaluating exact exchange is routine in molecular quantum chemical calculations performed with localized basis sets, the non-local nature of the exchange operator presents a major impediment to the efficient use of exact exchange in calculations that employ planewave basis sets. Non-orthogonal generalized Wannier functions (NGWFs) corresponding to planewave expansions of localized basis functions are an alternative form of basis set that can be used in quantum chemical calculations. The periodic nature of these functions renders them suitable for calculations of periodic systems, while the contraction of sets of planewaves into individual basis functions reduces the number of variational parameters, permitting the construction and direct diagonalization of the Fock matrix. The present study examines how NGWFs corresponding to Fourier series representations of conventional atom-centered basis sets can be used to evaluate exact exchange in periodic systems. Specifically, an approach for constructing the exchange operator with NGWFs is presented and used to perform Hartree-Fock calculations with a series of molecules in periodically repeated simulation cells. The results demonstrate that the NGWF approach is significantly faster than the EXX method, which is a standard approach for evaluating exact exchange in periodic systems.
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14 March 2017
Research Article|
March 13 2017
Exact exchange with non-orthogonal generalized Wannier functions
Jeff Mountjoy;
Jeff Mountjoy
Department of Chemistry,
Queen’s University
, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada
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Michelle Todd;
Michelle Todd
Department of Chemistry,
Queen’s University
, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada
Search for other works by this author on:
Nicholas J. Mosey
Nicholas J. Mosey
a)
Department of Chemistry,
Queen’s University
, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada
Search for other works by this author on:
Jeff Mountjoy
Michelle Todd
Nicholas J. Mosey
a)
Department of Chemistry,
Queen’s University
, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada
a)
Electronic mail: [email protected]
J. Chem. Phys. 146, 104108 (2017)
Article history
Received:
November 22 2016
Accepted:
February 17 2017
Citation
Jeff Mountjoy, Michelle Todd, Nicholas J. Mosey; Exact exchange with non-orthogonal generalized Wannier functions. J. Chem. Phys. 14 March 2017; 146 (10): 104108. https://doi.org/10.1063/1.4977783
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