The ab initio quantum mechanical charge field molecular dynamics simulation technique was applied for the first time to an electronically excited system, namely hydrated Li(I). This approach does not only provide data for the influence of electronic excitation on structure and composition of the hydrate, but also leads to a spectrum for the excitation band including rotational, translational and vibrational energy transfers. The first excitation band for Li(I) in water peaks at 13.1 eV. The excitation leads to reduced coordination numbers of first and second hydration shell and stabilises the first and labilises the second shell. (C) 2011 Elsevier B. V. All rights reserved.