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Article Analytic energy, gradient, and hessian of electrostatic embedding QM/MM based on electrostatic potential tted atomic charges scaling linearly with the MM subsystem size

Abstract : Electrostatic potential tting method (ESPF) is a powerful way of dening atomic charges derived from quantum density matrices tted to reproduce a quantum mechanical charge distribution in the presence of an external electrostatic potential. These can be used in the Hamiltonian to dene a robust and ecient electrostatic embedding QM/MM method. The original formulation of ESPF QM/MM contained two main approximations, namely, the neglect of grid derivatives and the non-conservation of the total QM charge. Here, we present a new ESPF atomic charge operator which solves these drawbacks at virtually no extra computational cost. The new charge operators employ atom-centered grids and conserve the total charge when traced with the density matrix. We present an ecient and easy-to-implement analytic form for the energy, gradient, and hessian that scale linearly with the MM subsystem size. We show that grid derivatives and charge conservation are fundamental to preserve the translational invariance properties of energies and its derivatives and exact conditions to be satised by the atomic charge derivatives. As proof of concept, we compute the transition state that leads to the formation of hydrogen peroxide during cryptochrome's reoxidation reaction. Last, we show that the construction of the full QM/MM hessian scales linearly with the MM subsystem size.
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https://hal-amu.archives-ouvertes.fr/hal-03015736
Contributor : Miquel Huix-Rotllant <>
Submitted on : Friday, November 20, 2020 - 9:05:54 AM
Last modification on : Saturday, November 21, 2020 - 3:22:17 AM

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Miquel Huix-Rotllant, Nicolas Ferré. Article Analytic energy, gradient, and hessian of electrostatic embedding QM/MM based on electrostatic potential tted atomic charges scaling linearly with the MM subsystem size. Journal of Chemical Theory and Computation, American Chemical Society, In press, ⟨10.1021/acs.jctc.0c01075⟩. ⟨hal-03015736⟩

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