and 
electrons in a hydrated benzene
http://orcid.org/0000-0002-4412-4115
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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.