Communication: Variational many-body expansion: Accounting for exchange repulsion, charge delocalization, and dispersion in the fragment-based explicit polarization method

A fragment-based variational many-body (VMB) expansion method is described to directly account for exchange repulsion, charge delocalization (charge transfer) and dispersion interactions in the explicit polarization (X-Pol) method. The present VMB/X-Pol approach differs from other fragment molecular orbital (FMO) techniques in two major aspects. First, the wave function for the monomeric system is variationally optimized using standard X-Pol method, as opposed to the iterative update procedure adopted in FMO. Second, the mutual polarizations in the dimeric terms are also variationally determined, whereas single-point energy calculations of the individual dimers embedded in a static monomer field are used in FMO. The second-order (two-body) VMB (VMB2) expansion method is illustrated on a series of water hexamer complexes and one decamer cluster, making use of Hartree-Fock theory, MP2, and the PBE1 and M06 density functionals to represent the monomer and dimer fragments. The computed binding energies are within 2 kcal/mol of the corresponding results from fully delocalized calculations. Energy decomposition analyses reveal specific dimeric contributions to exchange repulsion, charge delocalization, and dispersion. Since the wave functions for one-body and all two-body terms are variationally optimized in VMB2 and X-Pol, it is straightforward to obtain analytic gradient without the additional coupled-perturbed Hartree-Fock step. Thus, the method can be useful for molecular dynamics simulations. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3688232]