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Fast noniterative orbital localization for large molecules

Aquilante, Francesco LU ; Pedersen, Thomas LU ; Sanchez de Meras, Alfredo and Koch, Henrik (2006) In Journal of Chemical Physics 125(17).
Abstract
We use Cholesky decomposition of the density matrix in atomic orbital basis to define a new set of occupied molecular orbital coefficients. Analysis of the resulting orbitals ("Cholesky molecular orbitals") demonstrates their localized character inherited from the sparsity of the density matrix. Comparison with the results of traditional iterative localization schemes shows minor differences with respect to a number of suitable measures of locality, particularly the scaling with system size of orbital pair domains used in local correlation methods. The Cholesky procedure for generating orthonormal localized orbitals is noniterative and may be made linear scaling. Although our present implementation scales cubically, the algorithm is... (More)
We use Cholesky decomposition of the density matrix in atomic orbital basis to define a new set of occupied molecular orbital coefficients. Analysis of the resulting orbitals ("Cholesky molecular orbitals") demonstrates their localized character inherited from the sparsity of the density matrix. Comparison with the results of traditional iterative localization schemes shows minor differences with respect to a number of suitable measures of locality, particularly the scaling with system size of orbital pair domains used in local correlation methods. The Cholesky procedure for generating orthonormal localized orbitals is noniterative and may be made linear scaling. Although our present implementation scales cubically, the algorithm is significantly faster than any of the conventional localization schemes. In addition, since this approach does not require starting orbitals, it will be useful in local correlation treatments on top of diagonalization-free Hartree-Fock optimization algorithms. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
125
issue
17
publisher
American Institute of Physics
external identifiers
  • wos:000241830200005
  • scopus:33750712378
ISSN
0021-9606
DOI
10.1063/1.2360264
language
English
LU publication?
yes
id
a5ff4d4b-36ec-4aa2-b0e6-8345a1eb7124 (old id 378367)
date added to LUP
2007-08-27 12:36:13
date last changed
2019-03-19 01:34:54
@article{a5ff4d4b-36ec-4aa2-b0e6-8345a1eb7124,
  abstract     = {We use Cholesky decomposition of the density matrix in atomic orbital basis to define a new set of occupied molecular orbital coefficients. Analysis of the resulting orbitals ("Cholesky molecular orbitals") demonstrates their localized character inherited from the sparsity of the density matrix. Comparison with the results of traditional iterative localization schemes shows minor differences with respect to a number of suitable measures of locality, particularly the scaling with system size of orbital pair domains used in local correlation methods. The Cholesky procedure for generating orthonormal localized orbitals is noniterative and may be made linear scaling. Although our present implementation scales cubically, the algorithm is significantly faster than any of the conventional localization schemes. In addition, since this approach does not require starting orbitals, it will be useful in local correlation treatments on top of diagonalization-free Hartree-Fock optimization algorithms.},
  author       = {Aquilante, Francesco and Pedersen, Thomas and Sanchez de Meras, Alfredo and Koch, Henrik},
  issn         = {0021-9606},
  language     = {eng},
  number       = {17},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Fast noniterative orbital localization for large molecules},
  url          = {http://dx.doi.org/10.1063/1.2360264},
  volume       = {125},
  year         = {2006},
}