The numerical condition of electron correlation theories when only active pairs of electrons are spin-unrestricted.
The use of spin-unrestriction with high-quality correlation theory, such as coupled-cluster (CC) methods, is a common practice necessary to obtain high-quality potential energy surfaces. While this typically is a useful approach, we find that in the unrestricted limit of ROHF fragments (the unrestricted in active pair orbitals) the CC equations are singular if only the strongly correlated electrons are considered. Unstable amplitudes which do not represent the physics of the problem are easily found and could be unwittingly accepted without inspection. We use stability analysis and the condition number of the CC doubles Jacobian matrix to examine the problem, and present results for several molecular systems with a variety of unrestricted cluster models. Finally a regularization of the CC equations is proposed, using a dynamic penalty function, which allows us to apply CC, and Lagrangian gradient formulas even in the singular limit.
Lawler
Keith V
KV
Department of Chemistry and Chemical Sciences Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720, USA. keith@bastille.cchem.berkeley.edu
Parkhill
John A
JA
Head-Gordon
Martin
M