Vibronic Coupling Drives the Ultrafast Internal Conversion in a Functionalized Free-Base Porphyrin.

Internal conversion (IC) is a common radiationless transition in polyatomic molecules. Theory predicts that molecular vibrations assist IC between excited states, and ultrafast experiments can provide insight into their structure-function relationship. Here we elucidate the dynamics of the vibrational modes driving the IC process within the Q band of a functionalized porphyrin molecule. Through a combination of ultrafast multidimensional spectroscopies and theoretical modeling, we observe a 60 fs Q y -Q x IC and demonstrate that it is driven by the interplay among multiple high-frequency modes. Notably, we identify 1510 cm -1 as the leading tuning mode that brings the porphyrin to an optimal geometry for energy surface crossing. By employing coherent wave packet analysis, we highlight a set of short-lived vibrations (1200-1400 cm -1 ), promoting the IC within ≈60 fs. Furthermore, we identify one coupling mode (1350 cm -1 ) that is responsible for vibronic mixing within the Q states. Our findings indicate that porphyrin-core functionalization modulates IC effectively, offering new opportunities in photocatalysis and optoelectronics.