Calculation of Excited State Internal Conversion Rate Constant Using the One-Effective Mode Marcus-Jortner-Levich Theory.

In this article, the one-effective mode Marcus-Jortner-Levich (MJL) theory and the classical Marcus theory for electron transfer were applied to estimate the internal conversion rate constant, k IC , of organic molecules and a Ru-based complex, all belonging to the Marcus inverted region. For this, the reorganization energy was calculated using the minimum energy conical intersection point to account for more vibrational levels, correcting the density of states. The results showed good agreement with experimental and theoretically determined k IC , with a small overestimation by the Marcus theory. Also, molecules less dependent on the solvent effects, like benzophenone, presented better results than molecules with an expressive dependence, like 1-aminonaphthalene. Moreover, the results suggest that each molecule possesses unique normal modes leading to the excited state deactivation that does not necessarily match the X-H bond stretching, as previously suggested.