Electron-Vibrational Coupling and Fluorescence Spectra of Tetra-, Penta-, and Hexacoordinated Chlorophylls c1 and c2

Chlorophylls (Chls) are a group of pigments related to light absorption, excitation energy, and electron transfer in photosynthetic complexes. Given the importance of intramolecular nuclear motion for these electronic processes, many experimental studies were performed in order to relate its coupling to electronic coordinates of these pigments, but a detailed analysis is still lacking for isolated Chls c1 and c2. To gain insight into the intramolecular motion and fluoroscence spectra of these two pigments in tetra-, penta-, and hexacoodinated states, we performed a quantum chemical study based on density functional theory and multimode harmonic approximation with displaced, distorted, and rotated normal modes. In order to benchmark the employed methods, we simulated the high-resolution fluorescence spectra of tetracoodinated Chls a, b, and d and compared them with available experimental spectra obtained with fluorescence line-narrowing techniques. Although the experimental spectra were obtained for ligand coordinated Chls, qualitatively good agreement was found between the simulated and experimental spectra. Almost all resonances were reproduced in the spectroscopically interesting region from 200 to 1700 cm(-1). The significance of mode distortion and rotation for the simulated spectra is discussed. The fluorescence spectra of Chls c1 and c2 consist of a group of peaks in the 200-450 cm(-1) spectral range, a group of weak peaks from 700 to 1000 cm(-1), and a large group of strong peaks from 1100 to 1600 cm(-1). Ligand effects are also addressed, and a mode is identified as a sensitive probe for the coordination state of Chls c1 and c2.