Premium
On the Position of the Highest Occupied Molecular Orbital in Aqueous Solutions of Simple Ions
Author(s) -
Hunt Patricia,
Sprik Michiel
Publication year - 2005
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500006
Subject(s) - ion , aqueous solution , chemistry , limiting , molecule , homo/lumo , molecular orbital , electron , solvent , atomic physics , simple (philosophy) , computational chemistry , molecular physics , analytical chemistry (journal) , physics , quantum mechanics , organic chemistry , mechanical engineering , philosophy , epistemology , engineering
The energies of the highest occupied molecular orbital (HOMO) of four simple microsolvated aqua ion clusters (Na + , Ag + , Cl − , CN − ) are computed for varying numbers of water molecules. Extrapolating to infinite hydration numbers we find that these energies approach a value of −6 eV. This limiting one‐electron energy is within a margin of ±1 eV independent of the character of the ion and is 4 eV lower compared to the estimate obtained for the HOMO energy of the ions in aqueous solution under periodic boundary conditions. We argue that this discrepancy must the attributed to a shift in the reference of the one‐electron potential of the periodic solvent model.