Abstract
In a recent work, we performed free-energy analyses for hydration of benzene by conducting QM/MM-ER simulations, where the total solvation free energy was decomposed into contributions and . is the solvation free energy of the solute with a fixed electron density and is the residual free energy due to the electron density polarisation in solution. We, further, decomposed the free energies due to electron density fluctuations in aromatic solutes in aqueous solutions into contributions from and orbitals. We note, however, that the decompositions will not be validated when the polarisations of orbitals seriously couple with those of orbitals. In this paper, we study a correlation matrix between polarisations of and orbitals through QM/MM simulations to assess the coupling strength among the orbitals. We found that the electron density polarisation is dominated by the polarisation arising from transfers between the orbitals lying in the HOMO–LUMO region. Thus, the polarisation of electrons hardly couples with that from orbitals, which justifies our decomposition analyses.
Notes
No potential conflict of interest was reported by the authors.