Excited-state normal-mode analysis: The case of porphyrins

We systematically applied excited-state normal mode analysis to investigate and compare the relaxation and internal conversion dynamics of a free-base porphyrin (BP) with those of a novel functional porphyrin (FP) derivative. We discuss the strengths and limitations of this method and employ it to predict very different dynamical behaviors of the two compounds and to clarify the role of high reorganization energy modes in driving the system toward critical regions of the potential energy landscape. We identify the modes of vibrations along which the energy gap between two excited-state potential energy surfaces within the Q band manifold may vanish and find that the excess energy to reach this "touching" region is significantly reduced in the case of FP (0.16 eV) as compared to the one calculated for BP (0.92 eV). Our findings establish a link between the chemical functionalization and the electronic and vibrational structure that can be exploited to control the internal conversion pathways in a systematic way.