Among various models that incorporate solvation effects into first-principles-based electronic structure theory such as density functional theory (DFT), the average solvent electrostatic potential/molecular dynamics (ASEP/MD) method is particularly advantageous. This method explicitly includes the nature of complicated solvent structures that is absent in implicit solvation methods. Because the ASEP/MD method treats only solvent molecule dynamics, it requires less computational cost than the conventional quantum mechanics/molecular mechanics (QM/MM) approaches. Herein, we present a real-space rectangular grid-based method to implement the mean-field QM/MM idea of ASEP/MD to plane-wave DFT, which is termed "DFT in classical explicit solvents", or DFT-CES. By employing a three-dimensional real-space grid as a communication medium, we can treat the electrostatic interactions between the DFT solute and the ASEP sampled from MD simulations in a seamless and straightforward manner. Moreover, we couple a fast and efficient free energy calculation method based on the two-phase thermodynamic (2PT) model with our DFT-CES method, which enables direct and simultaneous computation of the solvation free energies as well as the geometric and electronic responses of a solute of interest under the solvation effect. With the aid of DFT-CES/2PT, we investigate the solvation free energies and detailed solvation thermodynamics for 17 types of organic molecules, which show good agreement with the experimental data. We further compare our simulation results with previous theoretical models and assumptions made for the development of implicit solvation models. We anticipate that our proposed method, DFT-CES/2PT, will enable vast utilization of the ASEP/MD method for investigating solvation properties of materials by using periodic DFT calculations in the future.
A Zn(ii)-amino acid MOF catalyst and its use for CO2fixation are reported, in addition to corresponding structure-topology-DFT studies.
Aromatic groups can engage in an interesting class of noncovalent interactions termed π−π interactions, which play a pivotal role in stabilizing a variety of molecular architectures, including nucleic acids, proteins, and supramolecular assemblies. When the aromatic compounds interact with each other in an aqueous environment, their association is facilitated by the hydrophobic effect−the trend of nonpolar solutes to aggregate in a polar solution. To develop an indepth understanding of hydrophobic association, we investigate in the present work π−π interactions in water, employing as a paradigm the benzene dimer. Using DFT-CES, a mean-field QM/MM method recently developed by our group, we describe the benzene solute at a quantum-mechanical level. Full consideration of detailed solute-electron density enables an optimal description of the solute−solvent interactions, leading to an accurate prediction of hydration free energies. In π-stacking of benzene, we find an entropic stabilization associated with the shrinkage of the solvent-excluded volume, which agrees with the theory of hydrophobic effect at subnanoscales. However, at the equilibrium binding distance of the benzene dimer, we find that the entropic stabilization nearly cancels out due to the enthalpic cost required for dewetting the internal space. Such an enthalpy−entropy compensation leads the association free energy to be predominantly dictated by the solute− solute interaction enthalpy. The present work offers new insight into the mechanistic role of water and the primary thermodynamic driving force of hydrophobic association.
The local temperatures of a metal nanostructure and its adsorbate carry essential information about the energy dissipation dynamics, calling for nanoscale thermometry techniques. Here we present a surface-enhanced Raman scattering (SERS) thermometry method providing an accurate local temperature of the adsorbates: we use the ratios of anti-Stokes (aS) and Stokes (S) SERS vibrational peaks at the limit of zero (0) probe laser intensity, extrapolated from the spectra acquired with varying laser intensities, as an internal reference of the spectrum− temperature correlation. This self-referencing removes most of the measurement bias and uncertainty created by the different electromagnetic enhancements in aS and S components of SERS spectra and enables reliable thermometry with an accuracy and a precision of <10 K. Using the method, we have quantified the photothermal heating of adsorbates on the surfaces of plasmon catalysts.
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