The roles of hydrogen bonds in the solvation of an excess electron and a lithium atom in water hexamer cluster at 150 K have been studied by means of ab initio molecular dynamics simulations. It is found that the hydrogen bonded structures of (H2O)(6)- and Li(H2O)(6) clusters are very different from each other and they dynamically evolve from one conformer to other along their simulation trajectories. The populations of the single acceptor, double acceptor, and free type water molecules are found to be significantly high unlike that in pure water clusters Free hydrogens of these type of water molecules primarily capture the unbound electron density in these clusters It is found that the binding motifs of the free electron evolve with time and the vertical detachment energy of (H2O)(6)- and vertical ionization energy of Li(H2O)(6) also change with time. Assignments of the observed peaks in vibrational power spectra are clone, and we found direct correlations between the time-averaged population of water molecules in different hydrogen bonding states and the spectral features The dynamical aspects of these clusters have also been studied through calculations of lime correlations of instantaneous stretch frequencies,of OH modes which are obtained from the simulation trajectories through a time series analysis.