6533b82efe1ef96bd1293441
RESEARCH PRODUCT
Fast noniterative orbital localization for large molecules
Alfredo Sánchez De MerásHenrik KochFrancesco AquilanteThomas Bondo Pedersensubject
Density matrixPhysicsBasis (linear algebra)Minor (linear algebra)General Physics and AstronomySTO-nG basis setsOrbital calculationsUNESCO::FÍSICA::Química físicaHF calculations ; Orbital calculationsPhysics and Astronomy (all)Atomic orbitalComputational chemistryMolecular orbitalOrthonormal basisStatistical physicsPhysical and Theoretical Chemistry:FÍSICA::Química física [UNESCO]HF calculationsCholesky decompositiondescription
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. © 2006 American Institute of Physics.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2006-01-01 | The Journal of Chemical Physics |