embedding; catalysis; electronic structure theory; solutions chemistry; quantum chemistry
Wilhelm Jan, VandeVondele Joost, Rybkin Vladimir V. (2019), Dynamics of the Bulk Hydrated Electron from Many-Body Wave-Function Theory, in Angewandte Chemie International Edition
, 58(12), 3890-3893.
Hutter Jürg, Wilhelm Jan, Rybkin Vladimir V., Ben Mauro Del, VandeVondele Joost (2018), Handbook of Materials ModelingMethods: Theory and Modeling
, Springer International Publishing, Cham.
Accurate and efficient methods for condensed-phase quantum chemistry are pivotal for understanding catalytic activity, biochemistry, solutions chemistry and surface chemistry. For chemistry, bond breaking/formation is the most important issue. However, the field of computational quantum science in the condensed phase is mostly shaped under the agenda of solid state physics, focusing on the band structure.Condensed-phase chemistry problems are attacked by the physicist's methods (mostly by the density functional theory, DFT}), often producing ambiguous results. Fortunately, molecular quantum chemistry community has realized that bond breaking requires a special approach taking the so called ``static'' correlation into account and has developed a successful tradition for this.However, the corresponding methods (known as multiconfigurational or multireference) designed for molecules are barely applicable to the condensed phase due to unfavorable computational scaling character. This proposal aims at improving the accuracy and efficiency of condensed-phase quantum chemistry using the evolving quantum (density functional and density matrix) embedding theories. Those are based on the partitioning of the quantum system into the chemically active fragment (fragments) and the embedding environment, which are handled at different levels of electronic structure theory: the former with expensive multiconfigurational ones, whereas the latter -- with the DFT or other less expensive methods. The goal of the applicant is to bring the so far exclusive embedding theories to a new level of usability by improving the theoretical formalisms, algorithms and software implementations based on the popular CP2K electronic structure program interfaced to multiconfigurational quantum chemistry codes. The resulting programs will be presented to the community and their functionality will be demonstrated by relevant applications including catalytic reactions on the anatase surface and nucleophilic substitution in aqueous medium. Successful completion of the project will be a landmark in establishing a new paradigm of the condensed-phase quantum chemistry, providing realistic accuracy for realistic chemical systems.