Index of multi-determinantal and multi-reference character in coupled-cluster theory
A full configuration interaction calculation (FCI) ultimately defines the innate molecular orbital description of a molecule. Its density matrix and the natural orbitals obtained from it quantify the difference between having N-dominantly occupied orbitals in a reference determinant for a wavefuncti...
Gespeichert in:
Veröffentlicht in: | The Journal of chemical physics 2020-12, Vol.153 (23), p.234103-234103 |
---|---|
Hauptverfasser: | , , , , , , |
Format: | Artikel |
Sprache: | eng |
Schlagworte: | |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
Zusammenfassung: | A full configuration interaction calculation (FCI) ultimately defines the innate molecular orbital description of a molecule. Its density matrix and the natural orbitals obtained from it quantify the difference between having N-dominantly occupied orbitals in a reference determinant for a wavefunction to describe N-correlated electrons and how many of those N-electrons are left to the remaining virtual orbitals. The latter provides a measure of the multi-determinantal character (MDC) required to be in a wavefunction. MDC is further split into a weak correlation part and a part that indicates stronger correlation often called multi-reference character (MRC). If several virtual orbitals have high occupation numbers, then one might argue that these additional orbitals should be allowed to have a larger role in the calculation, as in MR methods, such as MCSCF, MR-CI, or MR-coupled-cluster (MR-CC), to provide adequate approximations toward the FCI. However, there are problems with any of these MR methods that complicate the calculations compared to the uniformity and ease of application of single-reference CC calculations (SR-CC) and their operationally single-reference equation-of-motion (EOM-CC) extensions. As SR-CC theory is used in most of today’s “predictive” calculations, an assessment of the accuracy of SR-CC at some truncation of the cluster operator would help to quantify how large an issue MRC actually is in a calculation, and how it might be alleviated while retaining the convenient SR computational character of CC/EOM-CC. This paper defines indices that identify MRC situations and help assess how reliable a given calculation is. |
---|---|
ISSN: | 0021-9606 1089-7690 |
DOI: | 10.1063/5.0029339 |