Relaxation processes of the energy-rich protonated water dimer H+(H2O)(2) were investigated by the ab initio molecular dynamics (AIMD) method. At first, the energy-rich H+(H2O)(2) was reproduced by simulating a collision reaction between the protonated water monomer H3O+ and H2O. Next it was collided with N-2 in order to observe the effects of intramolecular vibration redistribution and intermolecular energy transfer. Forty-eight AIMD simulations of the collision of H+(H2O)(2) with N-2 were performed by changing the initial orientation and the time interval between two collisions. It was revealed that the amount of energy transferred from H+(H2O)(2) to N-2 decreased the longer the time interval. The relationship between the intermolecular energy transfer and the vibrational states was examined with the use of an energy-transfer spectrogram (ETS), which is an analysis technique combining energy density analysis and short-time Fourier transform. The ETS demonstrates a characteristic vibrational mode for the energy transfer, which corresponds to the stretching of the hydrogen bond between H+(H2O)(2) and N-2 in an active complex.