Mechanisms of IR amplification in radical cation polarons.

ABSTRACT: Break down of the Born-Oppenheimer approximation is caused by mixing of electronic and vibrational transitions in the radical cations of some conjugated polymers, resulting in unusually intense vibrational bands known as infrared active vibrations (IRAVs). Here, we investigate the mechanism of this amplification, and show that it provides insights into intramolecular charge migration. Spectroelectrochemical time-resolved infrared (TRIR) and two-dimensional infrared (2D-IR) spectroscopies were used to investigate the radical cations of two butadiyne-linked conjugated porphyrin oligomers, a linear dimer and a cyclic hexamer. The 2D-IR spectra reveal strong coupling between all the IRAVs and the electronic π-π* polaron band. Intramolecular vibrational energy redistribution (IVR) and vibration

SUBMITTER: Kendrick WJ 

PROVIDER: S-EPMC8150116 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature