Development of the FMO/RI-MP2 Fully Analytic Gradient Using a Hybrid-Distributed/Shared Memory Programming Model

The fully analytic gradient of the second-order Møller-Plesset perturbation theory (MP2) with the resolution-of-the-identity (RI) approximation in the fragment molecular orbital (FMO) framework is derived and implemented using a hybrid multilevel parallel programming model, a combination of the general distributed data interface (GDDI) and the OpenMP API. The FMO/MP2 analytic gradient contains three parts, i.e., the internal fragment component, the electrostatic potential (ESP) component, and the response terms. The RI approximation is applied to the internal fragment MP2 gradient term, whose MP2 densities and monomer MP2 Lagrangians are shared with the ESP and the response terms. The FMO/RI-MP2 analytic gradient implementation is validated against the numerical gradient (with errors ∼10^-6-10^-5 Hartree/Bohr) and the energy conservation in molecular dynamics (MD) simulations using NVE ensembles. The RI approximation introduces an error of ∼10^-5 Hartree/Bohr with a speedup of 4.0-8.0× compared with the currently available GDDI FMO/MP2 gradient. The node linear scaling of the fragmentation framework due to multilevel parallelism is well-preserved and is demonstrated in single-point gradient calculations of large water clusters (e.g., 1120 and 2165 molecules) using 300-800 KNL compute nodes with a parallel efficiency of more than 90%.