Abstract: Two opposite conclusions are known on the symmetry of the vector coupling coefficients (VCCs), amn and bmn, in the restricted open-shell Hartree-Fock (ROHF) method. The first one states that the VCCs are symmetric for all spectroscopic terms, i.e., amn = anm and bmn = bnm. An opposing statement is that the "non-Roothaan" terms, arising from the degenerate open-shell electronic configuration γN, can be characterized by non-symmetric VCCs matrices only: ‖amn‖ ≠ ‖anm,‖ ‖bmn‖ ≠ ‖bnm‖. This article presents a detailed analysis of the VCCs symmetry problem. A general approach to the VCCs determination has been developed leading to non‐symmetric VCCs for γN systems with γ ≥ 3. The main purpose of this work is to eliminate the contradiction arising in the ROHF theory when the latter is applied to highly symmetric open‐shell molecules and atoms.

Cite: Plakhutin B.N.
Coupling Coefficients "Symmetry Dilemma" in the Restricted Open-Shell Hartree-Fock Method
Journal of Mathematical Chemistry. 1997. V.22. N2-4. P.203-233. DOI: 10.1023/A:1019184100245 WOS Scopus РИНЦ ANCAN OpenAlex

Dates:

Submitted:	Apr 1, 1997
Accepted:	Oct 21, 1997
Published print:	Dec 1, 1997

Identifiers:

Web of science:	WOS:000072558900007
Scopus:	2-s2.0-0039415155
Elibrary:	13272099
Chemical Abstracts:	1998:223650
Chemical Abstracts (print):	128:313066
OpenAlex:	W143978712

Citing:

DB	Citing
Web of science	5
Scopus	7
Elibrary	7
OpenAlex	7

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