Exactly Embedded Density Functional Theory: A New Paradigm for the First-principles Modeling of Reactions in Complex Systems.

摘要

Our ARO-supported work includes key contributions to the development of rigorous quantum embedding methods for the calculation of ground- and excited-state potential energy surfaces. Quantum embedding has long been recognized as a promising strategy for vastly reducing the cost of rigorous electronic structure theory calculations. However, prior to our work in this area, density functional and wavefunction embedding approaches were only applicable to weakly interacting systems, a severe constraint that excluded essentially all condensed-phase and reactive chemical applications. By developing both inversion-based and projection-based strategies to enable accurate embedding in the context of strongly interacting (i.e., covalently or hydrogen-bonded) systems, we have expanded the applicability of quantum embedding methodologies, an area of intense interest. In addition to developing new algorithms and software, we have demonstrated that our approach enables simulation of large systems with sub-linear scaling of the required computational time; and we have further demonstrated that it dramatically reduces the cost of accurately describing transition-metal complexes and large molecules and clusters. This work opens new doors for the accurate description of decomposition, catalytic, and electronically non-adiabatic processes in complex systems. This research meets the aims of the Army Research Office by significantly advancing the scope and accuracy of first-principles molecular simulations in complex, reactive systems.