Abstract:
We present a new quantum mechanics/molecular mechanics (QM/MM) embedding approach for systems with directional polar covalent bonds. This "covalent elastic polarizable environment" (covEPE) scheme features a variational treatment of an energy expression that includes all degrees of freedom of both the QM region (the "cluster") and the MM regions (the "environment"). The method completely and explicitly includes both the electrostatic and mechanical interactions between a QM model cluster and its environment. Monovalent pseudoatoms that represent real atoms of the material saturate the dangling bonds of the cluster; these pseudoatoms belong simultaneously to the QM and MM regions. For a correct description of a pure silica environment, we constructed a new force field of the shell-model type based on potential derived charges instead of formal charges. We implemented the covEPE approach in the density functional program ParaGauss and applied it to pure-silica and Al-containing chabazite, employing a generalized gradient approximation. These applications showed that calculated structural parameters and OH frequencies of bridging hydroxyl groups reproduce experimental data with good accuracy compared to other contemporary computational methods.