Multireference Approaches to Spin‐State Energetics of Transition Metal Complexes Utilizing the Density Matrix Renormalization Group

Abstract

AbstractThe accurate and reliable calculation of different electronic states in transition metal systems is a persistent challenge for theoretical chemistry. The widespread use of density functional theory for computing the relative energies of states with different spin in transition metal complexes not only has not discouraged, but often, owing to its limitations, has motivated the development and refinement of first‐principles wavefunction–based methods, including both single‐reference and multireference approaches. A significant boost for the latter has been the emergence of the density matrix renormalization group (DMRG) as a reliable tool in applied quantum chemistry. By enabling the use of larger active spaces than conventionally possible, DMRG has opened up areas of transition metal chemistry that were previously inaccessible to multireference approaches. The present perspective provides an overview of representative studies that make use of DMRG methods and discusses recent applications to spin‐state energetics of transition metal systems. These range from mononuclear to exchange‐coupled systems that define an important emerging field of DMRG applications. Major achievements are highlighted and potential pitfalls are identified with a view toward future methodological developments as well as extensions in the applicability of DMRG‐based approaches to problems of spin‐state energetics and exchange‐coupling in transition metal chemistry.