Paradoxical meta-GGA behavior in TM complexes

Prediction of spin-state ordering is essential for understanding catalytic activity and designing functional materials. Semilocal DFT can suffer from self-interaction errors that give rise to systematic bias for low-spin states. We recently identified surprising behavior from incorporation of higher-order terms (i.e., in a meta-GGA). By employing a diverse test set of isolated and complexed first-row transition metal ions, we discovered that meta-GGA exchange increases favor for high-spin states in strong field ligands but favors low-spin states in weak field ligands and ions. Interestingly, although GGAs have a strong bias for low-spin states in complexes, in the isolated ions, they appear to have a bias for high-spin states. This means that meta-GGA exchange improves over the standard GGA approximation for either strong field ligands or isolated ions but generally worsens GGA biases for intermediate field strengths. Check out more in our recent publication here!

About Us

The Kulik group focuses on the development and application of new electronic structure methods and atomistic simulations tools in the broad area of catalysis.

Our Interests

We are interested in transition metal chemistry, with applications from biological systems (i.e. enzymes) to nonbiological applications in surface science and molecular catalysis.

Our Focus

A key focus of our group is to understand mechanistic features of complex catalysts and to facilitate and develop tools for computationally driven design.

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