Multireference Character for 3d Transition-Metal-Containing Molecules.

Abstract

Coupled cluster and configuration interaction diagnostics have been examined in order to assess the reliability of single reference quantum methods for a series of 3d transition metal species including hydrides, nitrides, chalcogenides, halides, small clusters, coordination complexes, and metal dimers. Several means of diagnostics have been considered including T1 and D1 diagnostics (the Frobenius norm and matrix 2-norm of coupled cluster amplitudes for single excitations, respectively), C0(2) (the weight of leading configuration of a complete active space wave function), and %TAE (percent total atomization energy). T1 and D1 diagnostics are strongly correlated for certain metal-ligand bonding types. The use of T1 and D1 together with %TAE can provide more reliable assessment of the severity of nondynamical correlation than a single indicator can provide. New criteria, namely T1 > 0.05, D1 > 0.15, and |%TAE| > 10, are suggested to identify inorganic species with substantial nondynamical correlation. For these systems, energies and spectroscopic properties computed using single reference electronic correlation methods may suffer from large errors and unpredictable behavior. Conversely, a computation where a molecule is below one or more of these thresholds does not always imply domination by a single reference. Some historically pathological molecules such as Mn2 and Cr2 show T1 < 0.05 and D1 < 0.15. Current implementations of coupled cluster diagnostics may still be insufficient for categorization of molecules that have pronounced nondynamical correlation.