Density-dependent formulation of dispersion-repulsion interactions in hybrid QM/MM models.

Research paper by Carles C Curutchet, Lorenzo L Cupellini, Jacob J Kongsted, Stefano S Corni, Luca L Frediani, Arnfinn Hykkerud AH Steindal, Ciro Achille CA Guido, Giovanni G Scalmani, Benedetta B Mennucci

Indexed on: 15 Feb '18Published on: 15 Feb '18Published in: Journal of Chemical Theory and Computation


Mixed QM/MM models are widely used to explore the structure, reactivity and electronic properties of complex chemical systems. Whereas such models typically include electrostatics, and potentially polarization in so-called electrostatic and polarizable embedding approaches, respectively, non-electrostatic dispersion and repulsion interactions are instead commonly described through classical potentials despite their quantum mechanical origin. Here we present an extension of the Tkatchenko-Scheffler semiempirical van der Waals (vdWTS) scheme aimed at describing dispersion and repulsion interactions between quantum and classical regions within a QM/MM polarizable embedding framework. Starting from the vdWTS expression, we define a dispersion and a repulsion term, both of them density-dependent and consistently based on a Lennard-Jones-like potential. We explore transferable atom type-based parametrization strategies for the MM parameters, based on either vdWTS calculations performed on isolated fragments or on a direct estimation of the parameters from atomic polarizabilities taken from a polarizable force field. We investigate the performance of the implementation by computing self-consistent interaction energies for the S22 benchmark set, designed to represent typical non-covalent interactions in biological systems, in both equilibrium and out-of-equilibrium geometries. Overall, our results suggest that the present implementation is a promising strategy to include dispersion and repulsion in multiscale QM/MM models incorporating their explicit dependence on the electronic density.