Exchange Repulsion in Quantum Mechanical/Effective Fragment Potential Excitation Energies: Beyond Polarizable Embedding.

Hybrid quantum mechanical and molecular mechanical (QM/MM) approaches facilitate computational modeling of large biological and materials systems. Typically, in QM/MM, a small region of the system is modeled with an accurate quantum mechanical method and its surroundings with a more efficient alternative, such as a classical force field or the effective fragment potential (EFP). The reliability of QM/MM calculations depends largely on the treatment of interactions between the two subregions, also known as embedding. The polarizable embedding, which allows mutual polarization between solvent and solute, is considered to be essential for describing electronic excitations in polar solvents. In this work, we employ the QM/EFP model and extend the polarizable embedding by incorporating two short-range terms-a charge penetration correction to the electrostatic term and the exchange-repulsion term-both of which are modeled with one-electron contributions to the quantum Hamiltonian. We evaluate the accuracy of these terms by computing excitation energies across 37 molecular clusters consisting of biologically relevant chromophores surrounded by polar solvent molecules. QM/EFP excitation energies are compared to the fully quantum mechanical calculations with the configuration interaction singles (CIS) method. We find that the charge penetration correction diminishes the accuracy of the QM/EFP calculations. On the other hand, while the effect of exchange-repulsion is negligible for most ππ* transitions, the exchange-repulsion significantly improves description of nπ* transitions with blue solvatochromic shifts. As a result, addition of the exchange-repulsion term improves the overall accuracy of QM/EFP. Performances of QM/EFP models remain similar when excitation energies are modeled with cc-pVDZ and aug-cc-pVDZ basis sets.

Exchange-repulsion energy in QM/EFP.

The effective fragment potential (EFP) is a quantum mechanics (QM)-based model designed to accurately describe intermolecular interactions. Hybrid QM/EFP calculations combine quantum mechanical methods with an EFP embedding to study complex systems in which many-body effects are relevant. As in EFP-only calculations, non-bonded interactions between the QM region and EFP fragments are computed as a sum of electrostatic, polarization, dispersion, and exchange-repulsion energies. The exchange-repulsion term is a computational bottleneck of the EFP calculations. Here, we present a general procedure for computing the QM/EFP exchange-repulsion interactions based on one-electron contributions to the QM Hamiltonian, by using Gaussian functions to represent localized molecular orbitals of the effective fragments. The accuracy of the exchange-repulsion and total QM/EFP interaction energies is evaluated on a diverse set of dimers, including complexes from the S22 dataset of non-covalent interactions. In most cases, the QM/EFP energies are at least as accurate as corresponding EFP energies. A simple and computationally efficient form of the introduced QM/EFP exchange-repulsion term will facilitate further developments and applications of QM/EFP methods.