Efficiently Transplanting Potential Energy Interpolation Database between Two Systems: Bacteriochlorophyll Case with FMO and LH2 Complexes

Abstract

Generating a reliable potential energy surface (PES) is an important issue for studying the dynamics of any system with computational simulations. Interpolation mechanics/molecular mechanics (IM/MM) based on a PES interpolation scheme is a useful tool in that regard as it provides an accuracy of a quantum chemistry (QC) level while maintaining its computational cost comparable to conventional MM force fields. Despite this benefit, constructing the database for interpolation itself is still challenging and time-consuming. Here, we present a method with which we can construct the IM database of one system based on a preexisting data set for another related system. We adopt the case of constructing bacteriochlorophyll PESs for the light-harvesting 2 (LH2) complex by utilizing already available IM database for the BChls from the Fenna–Matthews–Olson (FMO) complex. In this method, the IM database from FMO is first transplanted to LH2 by considering BChl displacement vectors that take into account the geometry differences induced by the protein scaffolds. From this transplanted primitive database entries, a relatively small number of effective ones are selected by a survival process based on a genetic algorithm such that the IM energies evaluated at geometries in a conveniently collected prediction set can closely match with the reference QC energies. The selection process is expedited by using two different levels of basis sets for the QC calculations. To demonstrate the utility of the PES thus constructed, we carry out 1 ns of IM/MM dynamics simulations with the finally optimized BChl database for LH2. Indeed, the energy profiles of the snapshots are found to be closely matching with the reference QC calculation data, with only ∼0.07 eV of errors in the ground- and excited-state energies and ∼0.008 eV of errors in the transition energies. We also show that properly selecting data points is actually quite important for generating an IM PES toward performing molecular dynamics simulations.