Car-Parrinello molecular dynamics study of the intramolecular vibrational mode-sensitive double proton-transfer mechanisms in porphycene.

Car-Parrinello molecular dynamics simulations were carried out to help interpret proton-transfer processes observed experimentally in porphycene under thermodynamic equilibrium conditions (NVT ensemble) as well as during selective, nonequilibrium vibrational excitations of the molecular scaffold (NVE ensemble). In the NVT ensemble, the population of the trans form in the gas phase at 300 K is 96.5%, and of the cis-1 form is 3.5%, in agreement with experimental data. Approximately 70% of the proton-transfer events are asynchronous double proton transfers. According to the high resolution simulation data they consist of two single transfer events that rapidly take place one after the other. The average time-period between the two consecutive jumps is 220 fs. The gas phase reaction rate estimate at 300 K is 3.6 ps, which is comparable to experimentally determined rates. The NVE ensemble nonequilibrium ab initio MD simulations, which correspond to selective vibrational excitations of the molecular scaffold generated with high resolution laser spectroscopy techniques, exhibit an enhancing property of the 182 cm(-1) vibrational mode and an inhibiting property of the 114 cm(-1) one. Both of them influence the proton-transfer rate, in qualitative agreement with experimental findings. Our ab initio simulations provide new predictions regarding the influence of double-mode vibrational excitations on proton-transfer processes. They can help in setting up future programmable spectroscopic experiments for the proton-transfer translocations.