ArticleThe journal of physical chemistry letters2022
Interference between Franck-Condon and Herzberg-Teller Terms in the Condensed-Phase Molecular Spectra of Metal-Based Tetrapyrrole Derivatives.
Article in The journal of physical chemistry letters, 2022. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 6 papers.
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6 citing papers in PubMed, 23 citations in OpenAlex.
- Symmetry-Breaking Charge-Separation in a Subphthalocyanine Dimer Resolved by Two-Dimensional Electronic Spectroscopy.The journal of physical chemistry. C, Nanomaterials and interfaces · 2025Article
- Exploring the Role of Excited States' Degeneracy on Vibronic Coupling with Atomic-Scale Optics.ACS nano · 2024Article
- Deciphering between enhanced light emission and absorption in multi-mode porphyrin cavity polariton samples.Nanophotonics (Berlin, Germany) · 2024Article
- Assessing the Determinants of Cavity Polariton Relaxation Using Angle-Resolved Photoluminescence Excitation Spectroscopy.The journal of physical chemistry letters · 2024Article
- Pushing the Limit of Photo-Controlled Polymerization: Hyperchromic and Bathochromic Effects.Molecules (Basel, Switzerland) · 2024Article
- Decorrelated singlet and triplet exciton delocalization in acetylene-bridged Zn-porphyrin dimers.Chemical science · 2024Article
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4 authors at 2 institutions in 1 country.
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Abstract
The commonly used Franck-Condon (FC) approximation is inadequate for explaining the electronic spectra of compounds that possess vibrations with substantial Herzberg-Teller (HT) couplings. Metal-based tetrapyrrole derivatives, which are ubiquitous natural pigments, often exhibit prominent HT activity. In this paper, we compare the condensed phase spectra of zinc-tetraphenylporphyrin (ZnTPP) and zinc-phthalocyanine (ZnPc), which exhibit vastly different spectral features in spite of sharing a common tetrapyrrole backbone. The absorption and emission spectra of ZnTPP are characterized by a lack of mirror symmetry and nontrivial temperature dependence. In contrast, mirror symmetry is restored, and the nontrivial temperature-dependent features disappear in ZnPc. We attribute these differences to FC-HT interference, which is less pronounced in ZnPc because of a larger FC component in the dipole moment that leads to FC-dominated transitions. A single minimalistic FC-HT vibronic model reproduces all the experimental spectral features of these molecules. These observations suggest that FC-HT interference is highly susceptible to chemical modification.
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