Multiple bond breaking with APSG-based correlation methods

comparison of two approaches

Ádám Margócsy, Piotr Kowalski, Katarzyna Pernal, A. Szabados

Research output: Article

1 Citation (Scopus)

Abstract

Antisymmetrized product of strongly orthogonal geminals (APSG) Ansatz is a computationally economic wavefunction class with favorable formal properties. These include extensivity, variational determination of the wavefunction parameters or qualitatively correct description of single bond dissociation. Breaking multiple bonds or non-isolated single bonds results in fragments of incorrect spin state when computed by APSG. This has been identified as a potential problem in APSG-based linearized coupled cluster approach (LCC). An alternative correction scheme based on the extended random phase approximation (ERPA) is investigated from this point of view, in parallel with LCC. The two methods are compared formally. Potential energy curves and atomic spin by APSG-based LCC and ERPA are presented on illustrative examples for multiple bond breaking. Origin of the marked difference between the behavior of LCC and ERPA is explored.

Original languageEnglish
Article number159
JournalTheoretical Chemistry Accounts
Volume137
Issue number11
DOIs
Publication statusPublished - nov. 1 2018

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Correlation methods
Wave functions
Byproducts
products
Potential energy
approximation
Economics
economics
potential energy
fragments
dissociation
single bond
curves

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Multiple bond breaking with APSG-based correlation methods : comparison of two approaches. / Margócsy, Ádám; Kowalski, Piotr; Pernal, Katarzyna; Szabados, A.

In: Theoretical Chemistry Accounts, Vol. 137, No. 11, 159, 01.11.2018.

Research output: Article

Margócsy, Ádám ; Kowalski, Piotr ; Pernal, Katarzyna ; Szabados, A. / Multiple bond breaking with APSG-based correlation methods : comparison of two approaches. In: Theoretical Chemistry Accounts. 2018 ; Vol. 137, No. 11.
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