### Abstract

Various forms of the perturbation operator describing interactions between two many-electron systems are discussed. These operators result from different partitionings of the total hamiltonian. It is shown that the requirement of the correct permutational symmetry, i.e. that H^{(0)} and XXX possess the same symmetry as H, can only be satisfied if basis set expansion is not applied or if the underlying basis set is strictly complete. In matrix theories (second quantization) the usual form of the interaction operator can only be recovered if basis set superposition error (BSSE) terms are excluded from the hamiltonian.

Original language | English |
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Pages (from-to) | 39-46 |

Number of pages | 8 |

Journal | Journal of Molecular Structure: THEOCHEM |

Volume | 226 |

Issue number | 1-2 |

DOIs | |

Publication status | Published - Jan 15 1991 |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry
- Computational Theory and Mathematics
- Atomic and Molecular Physics, and Optics

### Cite this

**On the perturbation operator in ab initio theories of intermolecular interactions.** / Surján, P.

Research output: Contribution to journal › Article

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TY - JOUR

T1 - On the perturbation operator in ab initio theories of intermolecular interactions

AU - Surján, P.

PY - 1991/1/15

Y1 - 1991/1/15

N2 - Various forms of the perturbation operator describing interactions between two many-electron systems are discussed. These operators result from different partitionings of the total hamiltonian. It is shown that the requirement of the correct permutational symmetry, i.e. that H(0) and XXX possess the same symmetry as H, can only be satisfied if basis set expansion is not applied or if the underlying basis set is strictly complete. In matrix theories (second quantization) the usual form of the interaction operator can only be recovered if basis set superposition error (BSSE) terms are excluded from the hamiltonian.

AB - Various forms of the perturbation operator describing interactions between two many-electron systems are discussed. These operators result from different partitionings of the total hamiltonian. It is shown that the requirement of the correct permutational symmetry, i.e. that H(0) and XXX possess the same symmetry as H, can only be satisfied if basis set expansion is not applied or if the underlying basis set is strictly complete. In matrix theories (second quantization) the usual form of the interaction operator can only be recovered if basis set superposition error (BSSE) terms are excluded from the hamiltonian.

UR - http://www.scopus.com/inward/record.url?scp=0039748447&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0039748447&partnerID=8YFLogxK

U2 - 10.1016/0166-1280(91)80003-Q

DO - 10.1016/0166-1280(91)80003-Q

M3 - Article

AN - SCOPUS:0039748447

VL - 226

SP - 39

EP - 46

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

IS - 1-2

ER -