论文信息 - Two‐electron integrations in the Quantum Theory of Atoms in Molecules with correlated wave functions

Two‐electron integrations in the Quantum Theory of Atoms in Molecules with correlated wave functions

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

[1] Laurent Joubert,et al. Convergence of the electrostatic interaction based on topological atoms , 2001 .

[2] M. Blanco. Métodos cuánticos locales para la simulación de materiales iónicos. Fundamentos, algoritmos y aplicaciones , 1997 .

[3] F. Escudero,et al. Atoms in molecules , 1982 .

[4] Evert Jan Baerends,et al. A Quantum Chemical View of Density Functional Theory , 1997 .

[5] E. Davidson. N-representability of the electron pair density , 1995 .

[6] A. J. Coleman. THE STRUCTURE OF FERMION DENSITY MATRICES , 1963 .

[7] Paul L. A. Popelier,et al. Convergence of the multipole expansion for electrostatic potentials of finite topological atoms , 2000 .

[8] Á. M. Pendás,et al. Two-electron integrations in the quantum theory of atoms in molecules. , 2004, The Journal of chemical physics.

[9] K. Kay,et al. Bipolar Expansion for r12nYlm(θ12, φ12) , 1969 .

[10] Mark S. Gordon,et al. General atomic and molecular electronic structure system , 1993, J. Comput. Chem..