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Perturbation theory and electron correlation in extended systems: Cyclic polyene model
Author(s) -
Takahashi M.,
Paldus J.,
Čížek J.
Publication year - 1983
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.560240614
Subject(s) - hamiltonian (control theory) , electronic correlation , polyene , perturbation theory (quantum mechanics) , coupling constant , hubbard model , perturbation (astronomy) , physics , quantum mechanics , electron , mathematical physics , chemistry , mathematics , superconductivity , mathematical optimization , organic chemistry
The applicability of the finite‐order many‐body perturbation theory to the electron correlation problem in extended one‐dimensional systems is examined. The cyclic polyenes C N H N , N = 4ν + 2, ν = 1, 2, …, with the D Nh geometry as described by both the Pariser–Parr–Pople and Hubbard Hamiltonians, are employed to model the metallic‐like one‐dimensional systems. The second‐order perturbation theory contributions to the correlation energy are obtained with three different partitionings of the Hamiltonian (Hückel, M⊘ller–Plesset, and Epstein–Nesbet). The third‐ and fourth‐order contributions are also calculated in special cases. A comparison with other methods is given wherever available. For the Hubbard Hamiltonian the asymptotic behavior of the perturbation theory expansion is examined numerically. It is shown that the finite‐order perturbation expansion can provide reliable results for the correlation energy of one‐dimensional systems even in the correlation region which corresponds to the spectroscopically determined physical value of the coupling constant.