A diagnostic for determining the quality of single-reference electron correlation methods

2009/06/19 by Timothy J. Lee, Peter R. Taylor · 1,404 citations
Chemistry · Mathematics · Physics and Astronomy · #Advanced Chemical Physics Studies #Atomic orbital #Atomic physics #Chemistry #Configuration interaction #Correlation #Coupled cluster #Electron #Electronic correlation #Excited state #Full configuration interaction #Mathematics #Molecular orbital #Molecular spectroscopy and chirality #Molecule #Physics #Quantum mechanics #Spectroscopy and Quantum Chemical Studies #Statistical physics #Wave function

paper · open access · doi:10.1002/qua.560360824

published in International Journal of Quantum Chemistry 36(S23), 199-207 (Wiley)

openalex publication_date 2009/06/19 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

It was recently proposed that the Euclidian norm of the t1 vector of the coupled-cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appropriate. This diagnostic T1 is defined for use with self-consistent-field molecular orbitals and is invariant to the same orbital rotations as the coupled-cluster energy. T1 is investigated for several different chemical systems which exhibit a range of multireference behavior and is shown to be an excellent measure of the importance of nondynamical electron correlation and is far superior to C0 from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T1 (i.e., >0.02) probably indicates the need for a multireference electron correlation procedure.

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