Complementing Adiabatic\nand Nonadiabatic Methods To\nUnderstand Internal Conversion Dynamics in Porphyrin Derivatives

We analyze the internal conversion dynamics within the <i>Q</i><sub><i>y</i></sub> and <i>Q</i><sub><i>x</i></sub> excited states of both bare and functionalized\nporphyrins, which are known to exhibit significantly different time\nconstants experimentally. Through the integration of two complementary\napproaches, static calculation of per-mode reorganization energies\nand nonadiabatic molecular dynamics, we achieve a comprehensive understanding\nof the factors determining the different behavior of the two molecules.\nWe identify the key normal and essential modes responsible for the\npopulation transfer between excited states and discuss the efficacy\nof different statistical and nonstatistical analyses in providing\na full physics-based description of the phenomenon.