We examined several force field function forms using a novel density-based energy decomposition analysis (DEDA) method [J. Chem. Phys., 131, 164112 (2009)]. In comparison with other EDA approaches, this new DEDA method has the following two unique features:(1) It variationally calculates the total frozen density energy through constrained search; thus it enables a clean separation of the frozen density interaction energy from the density relaxation (i.e., polarization and charge transfer) contribution; and (2) the charge-transfer component is also calculated variationally based on the net electron flow in real space. These unique features enable the definition of each interaction component in DEDA to be more consistent with the typical physical picture employed in the classical force field description of intermolecular interactions. Using the DEDA results as reference, we have examined the performance of several electrostatic, vdW and polarization models and provided guidance for further force field development.

Examinations of force field function forms with density-based energy decomposition analysis

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.