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On the size consistency problem for anti-symmetrised geminal power wave function ansatz
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Theoretical Chemistry and Biology.
2022 (English)In: Molecular Physics, ISSN 0026-8976, E-ISSN 1362-3028, Vol. 120, no 9, article id e2049385Article in journal (Refereed) Published
Abstract [en]

It is shown that the accepted proof of the anti-symmetrised geminal power (AGP) wave functions lack of size consistency is not general enough to constitute a proof for the size consistency of the AGP wave function. The origin of the size consistency problem for AGP wave function in previous proofs is shown to stem from the perceived notion that the natural orbitals of the AGP always can be localised or guessed a priori. We here show that by applying different constraints on a more general geminal coefficient matrix that the ionised/electron-attached determinants can be eliminated in different ways in a spin-restricted basis, which is not possible in the accepted proof. Furthermore it is shown how different constraints on the coefficients in the geminal coefficient matrix can lead to different ionisation channels upon dissociation. We discuss the consequences of the generation of natural orbitals from the solution of the AGP using a more general coefficient matrix. Finally the modern use of the natural AGP as a reference function for another correlation method is discussed where improvements to the orbitals used in the modern AGP are suggested. 

Place, publisher, year, edition, pages
Informa UK Limited , 2022. Vol. 120, no 9, article id e2049385
Keywords [en]
Anti-symmetrised geminal power, geminal, size consistency, wave function parameterisation, Ionization, Molecular physics, Coefficient matrix, Consistency problems, Localised, Natural orbitals, Power, Power waves, Size-consistency, Wave function parameterization, Wave functions
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-322045DOI: 10.1080/00268976.2022.2049385ISI: 000766510000001Scopus ID: 2-s2.0-85126488752OAI: oai:DiVA.org:kth-322045DiVA, id: diva2:1714242
Note

QC 20221129

Available from: 2022-11-29 Created: 2022-11-29 Last updated: 2022-11-29Bibliographically approved

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Sørensen, Lasse K.

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CiteExportLink to record
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