A geminal theory based on the generalized electron pairing
As in the hierarchy of the Hartree–Fock theory in terms of spin symmetry, the extension of spin functions in a theory of two-electron units or geminal, was developed in this study. A trial wave function is constructed as an antisymmetrized product of geminals, in which singlet and triplet two-electr...
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| Published in: | The Journal of chemical physics 2023-06, Vol.158 (21), p.211104 |
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| Main Authors: | , |
| Format: | Article |
| Language: | eng |
| Subjects: | |
| Online Access: | Get full text |
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| Summary: | As in the hierarchy of the Hartree–Fock theory in terms of spin symmetry, the extension of spin functions in a theory of two-electron units or geminal, was developed in this study. A trial wave function is constructed as an antisymmetrized product of geminals, in which singlet and triplet two-electron functions are fully mixed. We present a variational optimization method for this generalized pairing wave function in the strong orthogonality condition. The present method is considered an extension of the antisymmetrized product of strongly orthogonal geminals or perfect pairing generalized valence bond methods, maintaining the compactness of the trial wave function. The obtained broken-symmetry solutions were similar to the unrestricted Hartree–Fock wave functions in terms of spin contamination while giving lower energy due to the inclusion of the electron correlation effect in geminals. The degeneracy of the obtained broken-symmetry solutions in the Sz space is reported for the tested four-electron systems. |
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| ISSN: | 0021-9606 1089-7690 |