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Recursive generation of natural orbitals in a truncated orbital space
Author(s) -
Li Xiangzhu,
Paldus Josef
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20654
Subject(s) - natural bond orbital , atomic orbital , complete active space , dipole , molecular orbital , linear combination of atomic orbitals , physics , space (punctuation) , quantum mechanics , chemistry , electron , density functional theory , computer science , molecule , operating system
We describe a procedure that generates a subset of low‐lying natural orbitals. It employs a small truncated orbital space, whose dimension is essentially given by the number of natural orbitals we wish to generate. The method is somewhat related to the numerical renormalization group technique. The resulting low‐lying, optimal natural orbitals can then be used in the computation of one‐electron properties, as well as of the energy via a small‐scale configuration interaction (CI), yielding improved potential energy and property surfaces over those obtained with the same method using Hartree–Fock orbitals. The procedure is illustrated on a DZP model of water, considering both the dipole moment and the total energy at the equilibrium and symmetrically stretched geometries. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005