 |
Center for Nonlinear Studies |
Efficient large-scale techniques are essential for computing multireference (strong) electronic correlation to describe electronic structure of organometallic chemistry. Systems that exhibit multireference correlation are often poorly described by single-reference methods like Hartree-Fock, DFT, and perturbation theories, but conventional multireference techniques often suffer from unfavorable scaling. As an alternative to those approaches, I describe recent advances in methodology and applications of two-electron reduced density-matrix (2- RDM) techniques that benefit from efficient polynomial scaling. Variational 2-RDM mechanics can compute electron correlation in systems that are too large for similar conventional multireference methods like configuration interaction (CI) and active-space techniques. These large-scale treatments of organometallic systems are important for describing the electronic structure of ligand-metal interactions, non-innocent ligand redox behavior, as well as accurately predicting geometric parameters. 2-RDM methods have proven useful in organometallic systems with extended π-networks such as vanadium-oxo pyridines and Mn-salen complexes, as well as species with large valence spaces such as CrF6. 2-RDM methods provide an avenue to describe multireference features of large-scale organometallic electronic structure in an efficient and systematic manner.
Host: Enrique Batista