| 概 要 |
Recent advances in photo emission spectroscopy of liquids and aqueous solutions by the group of Winter in Berlin (see e.g. J. Phys. Chem.
Lett. 2 (2011) 633) have posed a serious challenge to the electronic structure theory of aqueous solutions.
We now know where the vertical detachment levels (minus the vertical ionization potential (IP)) of aqueous solutes are located.
Of particular interest are the measurements of the vertical IP of small anions such as the hydroxide and halide anions.
Adding to this, the electrochemists seem to have finally agreed on the value of the absolute standard hydrogen electrode potential, which means we can directly compare vertical to adiabatic ionization potentials as obtained from redox potentials which gives us an estimate of the solvent reorganization.
It is now up to electronic structure calculation to reproduce and explain these results.
We have taken up this challenge using a combination of density functional theory based molecular dynamics (DFTMD) and free energy perturbation.
This talk is an outline of this development with particular emphasis on the key aspect which distinguishes the DFTMD approach from implicit solvent treatments, namely the interaction of the electronic states of the solute with the extended (band) states of liquid water.
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