J Chem Phys. 2011 Nov 28;135(20):204701. doi: 10.1063/1.3659702.
The Journal of chemical physics
B N Papas, J L Whitten
PMID: 22128946 DOI: 10.1063/1.3659702
The photochemistry of a solvated hydronium ion near a silver surface is investigated using ab initio self-consistent field and configuration interaction theory. Photoinduced electron attachment can occur at energies in the range of 1.1-1.2 eV depending upon the initial orientation of the hydronium relative to the silver surface. Rearrangement of solvating waters considerably reduces transition state barriers to dissociation on the excited-state potential energy surface, such that fast dissociation of the neutralized hydronium would occur with no barrier. Both the H and H(2) product channels are exothermic pathways on the excited state surface and in several instances exothermic compared to the energy of the initial structure.
