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Two‐electron integrations in the Quantum Theory of Atoms in Molecules with correlated wave functions
Author(s) -
Pendás A. Martín,
Francisco E.,
Blanco M. A.
Publication year - 2005
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20173
Subject(s) - wave function , atomic orbital , factorization , electron , quantum mechanics , density matrix , space (punctuation) , physics , atoms in molecules , order (exchange) , function (biology) , quantum , mathematics , computational chemistry , chemistry , mathematical physics , computer science , algorithm , evolutionary biology , biology , operating system , finance , economics
A recent method proposed to compute two‐electron integrals over arbitrary regions of space [Martín Pendás, A. et al., J Chem Phys 2004, 120, 4581] is extended to deal with correlated wave functions. To that end, we use a monadic factorization of the second‐order reduced density matrix originally proposed by E. R. Davidson [Chem Phys Lett 1995, 246, 209] that achieves a full separation of the interelectronic components into one‐electron terms. The final computational effort is equivalent to that found in the integration of a one determinant wave function with as many orbitals as occupied functions in the correlated expansion. Similar strategies to extract the exchange and self‐interaction contributions from the two‐electron repulsion are also discussed, and several numerical results obtained in a few test systems are summarized. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 344–351, 2005