Correlated electronic structure theory for challenging systems

Sergey Yu. Savrasov

Yubo Yang, Vitaly Gorelov, Carlo Pierleoni +2 more

Accurate prediction of the fundamental gap in insulators is a challenge for electronic structure theories. Electronic correlation and finite-size effects can significantly change the fundamental gap. Using quantum Monte Carlo, the authors show here that the fundamental gap can be calculated as the derivative discontinuity of the energy with respect to the electron density in the grand-canonical ensemble. Further, the finite-size error can be understood and corrected using information encoded in the electronic structure factor. The presented methodology applies for any explicitly correlated method.

Hong Yao

Konrad Heinrich Marti, Markus Reiher

Electronic structure theory faces many computational challenges in transition metal chemistry. Usually, density functional theory is the method of choice for theoretical studies on transition metal complexes and clusters mostly because it is the only feasible one, although its results are not systematically improvable. By contrast, multireference ab initio methods could provide a correct description of the electronic structure, but are limited to small molecules because of the tremendous computational resources required. In recent years, conceptually new ab initio methods emerged that turned out to be promising for theoretical coordination chemistry. We review and discuss two efficient parametrization schemes for the electronic wave function, the matrix product states and the complete-graph tensor network states. Their advantages are demonstrated at example transition metal complexes. Especially, tensor network states might provide the key to accurately describe strongly correlated and magnetic molecular systems in transition metal chemistry.

Steven Allan Kivelson